TW201219599A - Surface treatment liquid for zinc or zinc alloy plated steel sheet, zinc or zinc alloy plated steel sheet, and method of producing the steel sheet - Google Patents

Abstract

According to the present invention, a specific resin compound having a bisphenol frame, a cationic urethane resin emulsion, a silane coupling agent, an organic titanic chelate compound, a tetravalent vanadium compound, a molybdic acid compound, a fluorine compound and water are mixed in accordance with the predetermined proportion, and the pH value is adjusted to 4 to 5. Accordingly, a chrome-free surface treatment solution capable of forming a membrane on a surface of metal materials can be obtained. The membrane has excellent corrosion resistance in the bending part of the steel plate, solvent resistance, coating ability after alkali degreasing, and perspiration resistance.

Description

201219599 VI. Description of the Invention: [Technical Field] The present invention relates to an environmentally-friendly galvanized steel sheet which is most suitable for use in automobiles, home appliances, and building materials, and which is completely free of chromium during manufacturing and manufacturing. Production method. The present invention relates in particular to a surface treatment liquid useful for improving the sweat resistance and the like of a galvanized steel sheet. [Prior Art] For steel products for home appliances, steel sheets for building materials, and steel sheets for automobiles, the surface of galvanized steel sheets has been widely used for the purpose of improving corrosion resistance (white rust resistance, red resistance, and squeaking resistance). A complex acid blue steel plate was applied to a treatment liquid containing a complex acid, a heavy acid or a salt thereof as a main component. The complex acid salt treatment is excellent in the resistance to the recording, and can be relatively simple to carry out the treatment of the chromate treatment to make the material the public secrets (four) of the six secrets, but the price of chromium in the f Di system) The ΐ 铬 还原 还原 · 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原 还原And pollute the environment or the human body. However, the use of the movement of the L-ball environment problem, want to autonomously reduce the hexavalent chromium itself, the second material 2 to abandon the waste product of the waste chrome, or reduce the six =: = product as much as possible without the hexavalent due to In order to prevent white rust from being generated in galvanized steel sheets, a large number of 4 201219599 "two jpif have proposed a treatment technique that does not use chromate treatment, so-called chromium-free technology, such as the use of inorganic compounds, organic compounds, organic polymers. The material or the combination of 3 liters of materials can be smashed into the surface of the lining steel plate to treat the film. However, various useful technologies have been proposed so far, but with the introduction of these chromium-free technologies, new problems that have not been recognized so far have been confirmed. The first problem is the improvement of the financial property of the processing section of the surface treatment mirror zinc steel sheet. The surface-treated galvanized steel sheet is processed (cutting, bending, and welding of parts) ffij becomes the product 'but the surface-treated lining steel plate is bent, and the working time is added to the surface of the f-curved one. . ? That is, the surface-treated film is also stretched by the above-described one-folding process, so that the surface-treated film is damaged and the surface of the zinc is exposed, and the deterioration of the exposed portion is problematic. In the case of bending processing, the local damage is read by the face pressure, and the damage of the film and the county is continuously caused, so it is very difficult to obtain the impurity of the jade. The second problem is to ensure the solvent resistance of the surface treatment film. In the above processing steps, it is sometimes wiped off by the adhesion of the oil on the surface of the lyotropic film or the mark written by the mark ink. At this time, the surface treatment film peeling or whitish due to the solvent is frequently observed. The phenomenon of discoloration (whitening). In the case where the surface-treated film is peeled off, the resistance of the galvanized steel sheet cannot be sufficiently obtained, and the wire is reduced. The second problem of Beb & _ is to ensure the coating properties of the surface treatment film. The surface-treated galvanized steel sheet which has been processed as described above may be temporarily cleaned (alkali degreased) with an alkali cleaning agent or the like, and may be coated after being coated with a surface after degreasing. Therefore, the well-known literature on research has been conducted. The status quo is not able to find the special reading. The fourth lesson is to ensure that the resistance to blackening Ke. When it is used in an environment with high humidity or high temperature, it is easy to expose the steel plate to a long-term exposure to ^ a A m, which is liable to cause δ blackening on the surface of the plating. The blackening phenomenon is particularly remarkable when it has a coating layer containing a color, and therefore the surface treatment of the galvanized steel sheet is excellent in blackening resistance. &The film also needs the fifth subject in addition to the phenomenon of skin blackening in the county. When the person directly touches the second steel plate, he can recognize that the touch portion is resent with time: r-sexual sweat Adhered to the steel plate = plate = the adhesion of the sweat does not change to black, that is, the film is required to be as described above, and it is expected that various types of zinc steels with excellent characteristics will be implemented. Then, an aqueous solution of a diterpene, an alkyd resin, and a trialkoxy-neutralized oxidized u-meate is applied to a metal surface, and a dry film is formed to form a film. Further, in Patent Document 2 and Patent Document 3, a surface treatment method for imparting a water-soluble resin containing a ruthenium-based compound derivative to a metal material, and an aqueous solution using a styrene-butadiene compound are disclosed. Or a water-dispersible polymer to impart a corrosion resistance to a metal material. In the case of Patent Document 4, there is disclosed a technique in which a water-based resin, a colloidal dioxide 7, and a ruthenium-surface treatment agent are blended at a specific ratio. However, none of these technologies has developed a film which imparts a nicotine resistance to a chromic acid film. Except for the special offer 5 t reveals that there is a kind of compound containing petrolatum and sulfur-containing compounds, but it is not exaggerated after the degreasing. Patent Document 6 discloses a technique for treating a metal surface by using a treatment liquid containing an organic resin, a sulphur coupling agent, and a solid lubricant in an aqueous solution of a sulphuric acid clock, but the polymer is easily hardened by the (four) machine component. Therefore, the complexity of the fastening portion such as the folding process becomes insufficient. Further, since the alkali metal is contained, the secondary adhesion of the coating is poor. ^ Document 7 discloses the use of a resin aqueous solution containing a slow-drying diamine S ramie, an aqueous dispersion of an ethyl acrylate-unsaturated carboxylic acid copolymer, a dioxide: ^ and a coupling agent in a specific ratio. The technology of the resin film, but the solvent resistance or the processing part is not sufficient. And the special offer 8 towel reveals that there is a steel stomach plate with a film containing a certain ratio of amine vinegar 曰 / f β agent, inorganic colloidal compound and 矽 偶 coupling agent, designed on the premise of electric money coating, Although the resistance to electroplating of the coated and processed parts is not sufficient. Specialized in $:^:9, there is a surface treatment liquid which mixes Shi Xixuan coupling agent with amine vinegar resin to 2. 5~4.5, but the resistance difference after degreasing is not sufficient. I^Ho discloses a technique for forming a film by using a water-containing 201219599 ^fuuj^pif dispersion resin, an oxidation book, and an organic titanate s in a specific ratio, but the corrosion resistance of the processed portion is insufficient. Patent Document 11 and Patent Document 12 each disclose the use of a specific aqueous epoxy resin dispersion, an amine ester resin dispersion, a decane coupling agent, a phosphoric acid and/or a phosphoric acid compound, and one to five in one molecule. Although the treatment liquid of the fluorine compound forms a film, the alkali resistance is more or less insufficient, so that there is room for improvement in corrosion resistance or coating property after alkali degreasing. In addition, there is room for improvement in corrosion resistance or solvent resistance of the processed portion. Patent Document 13 discloses a technique for forming a film using a treatment liquid containing a specific resin compound, a vanadium compound, and a metal compound containing a specific metal. However, since alkali resistance is insufficient, corrosion resistance after alkali degreasing cannot be obtained. The problem of 'easy to yellow when heating separately' has not been solved. Patent Document 14 discloses a method of using a specific resin compound, a cationic amine g-containing resin having a cationic functional group, a decane coupling agent having a reactive functional group, a Ti compound, and an acid compound in a specific ratio. Membrane technology. According to this technique, a film excellent in stamina resistance or fingerprint resistance can be obtained. However, the corrosion resistance after alkali degreasing, the corrosion resistance of the processed portion, and the solvent resistance have not been studied, and there is room for improvement in suppression of such properties. Patent Document 15 discloses a technique relating to a surface treatment agent containing at least one aqueous resin selected from the group consisting of cationic and nonionic amine ester resins, a specific resin compound, a metal compound containing a specific metal, and water. However, there is no research on the alkali resistance and the corrosion resistance and solvent resistance of the processed portion, and these characteristics cannot be sufficiently obtained. 201219599 Patent Document 16 discloses a surface treatment using a cationic amine S, a condensate, a titanium, and a compound containing a specific metal in a specific ratio, but the solvent resistance or coating property is not studied. These features are not sufficient. PRIOR ART DOCUMENT Patent Document Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Patent Document 6 Patent Document 7 Patent Document 8 Patent Document 9 Patent Document 10 Patent Document 11 Patent Document 12 Patent [Patent Document 13] Patent Document 14 Patent Document 15 Patent Document 16 [Disclosure] The present invention has been made to solve the above-mentioned problems of the prior art, and the above-mentioned Japanese Patent Laid-Open Publication No. SHO-53-121034. Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent No. 3573307, Japanese Patent Laid-Open No. 2001-59184, Japanese Patent Laid-Open Publication No. 2003-155451, Japanese Patent Laid-Open No. 2006-8 Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 201219599 ^uu^^pif film, 'another ϋΓΓ 属 ( 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异 优异Galvanized steel sheet and its manufacturing. /, using the heart of the research to solve the above problems, the inventors and others carried out the potential: there = = two = specific proportion of specific resinized, page ionic amine Ester resin emulsion, 罝 牲 & & = = 禺 、 、 、 、 、 、 、 、 、 、 、 、 、 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定 特定It is not surprising that the resistance is excellent, and the film having excellent resistance to blackening and further rich in perspiration is also not deteriorated after storage. The present invention has been completed based on such findings, and its main constitution is as follows. a galvanized steel plate The surface treatment liquid used is characterized in that it satisfies the following conditions (1) to (6) and contains the following components and has a value of 4 to 5: a bisphenol skeleton represented by the following general formula (I) Resin compound (A); cationic amine ester resin emulsion (B) having at least one cationic functional group selected from the group consisting of a primary amino group to a tertiary amino group and a quaternary ammonium salt group; having a selected from the group consisting of active hydrogen-containing One or more decane couplings of at least one reactive functional group of an amine group, an epoxy group, a decyl group and a methacryloxy group; 201219599 4UUJ5pxf agent (c); an organic titanium chelating compound (D); Compound (E); molybdic acid compound (F); I compound (G); and water (H); (1) relative to the above resin compound (A), the above cationic amine ester resin emulsion (B) and the above decane The total solid content of the coupling agent (C) {(As) + (Bs) + (Cs)}, the solid content of the cationic amine ester emulsion (B) (Bs) by weight ratio [(BS) / {(AS + (Bs) + (Cs)}] is 0.10 to 0.30; (2) relative to the above resin compound (A), the above cationic amine ester resin emulsion (B), and the above decane The total solid content of the coupling agent (C) {(As) + (Bs) + (Cs)} 'The solid content (Cs) of the Shi Xi singer (C) is in the weight ratio [(Cs) / {(As + (Bs) + (Cs)}] is 0.60 to 0.85; (3) Titanium equivalent amount (DTi) with respect to the above-mentioned organic titanium chelate compound (D) 'solid of the above-mentioned alkane coupling agent (C) The amount of the component (Cs) is 50 to 70 in terms of a weight ratio {(Cs) / (DTi)}; (4) the amount of titanium (DTi) relative to the above-mentioned organic titanium chelate compound (d) 'the above-mentioned tetravalent vanadium The vanadium equivalent amount (ev) of the compound (E) is 0.30 to 0.50 in terms of a weight ratio {(Ev) / (DTi)}; (5) relative to the above resin compound (A), the above cationic amine 11 201219599 ester resin emulsion (B) and the total solid content of the above-mentioned decane coupling agent (C) {(As) + (Bs) + (Cs)}, the amount of the above-mentioned indium acid compound (F) (fm). ) is 0.003 to 0.03 in terms of a weight ratio [(Fm〇) / {(As) + (Bs) + (Cs)}]; (6) relative to the above resin compound (a), the above cationic amine ester resin emulsion ( B) and the total solid content of the above decane coupling agent (c) {(As) + (Bs) + (cs)}, and the fluorine-converted amount (Gf) of the fluorine compound (G) is a weight ratio [(GF) / {(As) + (Bs) + (Cs)}] counted as o.oi~ο. 1 ; [Chemical 1]

OH

In the formula (I), 1 and γ2 bonded to the benzene ring are each independently a hydrogen atom, and the sulfhydryl group represented by the above formula (II) or the formula (III) is a mercapto group per one benzene ring. The average of the substitution numbers is 〇2~i 〇; η represents an integer of 2 to 50; [Chemical 2] 12 201219599. —CH2~N, * · *(ii) [Chemical 3] + /R3 a ch2~n ^—E4 a— . · · (II ϊ) \r5 In the formula (II) and formula (III), 'R!, R2, r3, R4&r5 are independent of each other to represent a hydrogen atom, a carbon number 丨~-cut alkyl group Or a hydroxyalkyl group having a carbon number of 1 to 10, and A· represents a hydroxide ion or an acid ion. 2. The surface treatment liquid for a galvanized steel sheet according to the above 1, wherein the surface treatment liquid further contains a wax (W), and the solid content (Ws) of the wax (W) is relative to the resin compound (A) and The solid content of the cationic amine ester resin emulsion (B) is in the range of 0.2 to 0.4. 3. A method for producing a galvanized steel sheet, characterized in that the surface treatment liquid according to the above 1 or 2 has a deposition amount after drying of from 2 g/m 2 to 1.8 g/m 2 per side. It is coated on the surface of the galvanized steel sheet, and then dried at a sheet temperature of 50 ° C to 180 ° C. 4. A galvanized steel sheet having a surface treatment film having a surface adhesion amount of ο. g/m2 to 1.8 g/m2 on the surface, the galvanized steel sheet being characterized by: 13 201219599 40035pif the surface treatment film is The surface treatment liquid according to the above 1 or 2 is applied on the surface of the steel sheet to obtain a sheet temperature of 50 ° C to 180 ° C for drying.

Got it. X

[Effects of the Invention] According to the present invention, corrosion resistance, solvent resistance, coating property after alkali degreasing, and resistance can be formed in a bent portion which is not inferior to the chromate film and which is introduced into the manufacturing process. A black-denatured film which is excellent in sweat resistance and a chromium-free galvanized steel sheet which is more practical than the previous product can be obtained. [Embodiment] Hereinafter, the present invention will be specifically described. A steel sheet (processing original sheet) which is a substrate of the surface-treated steel sheet of the present invention is a galvanized steel sheet for household appliances, building materials, and automobile parts which is a cold-rolled steel sheet. The system is for the purpose of performance & the surface treatment of the present invention is preferably a galvanized steel sheet. The zinc-plated steel plate can be galvanized steel plate, galvanized steel plate, smelting alloy steel plate, galvanized iron alloy, galvanized __ plate, recording ^, and so on. Furthermore, the present invention can also be applied to a knot material such as a mine plate, a mine, a slab, or a slab, but is preferably applied to a steel plate. In addition, the plated steel plate may be added with a small amount of Ni or Co in the plating for the purpose of blackening the zinc-zinc steel plate, or may be made by using an acid or a miscellaneous water surface containing Fe. Made of galvanized steel. The surface of the present invention is explained by the surface analysis of the touch. The surface treatment liquid of the invention is characterized by comprising (4) a resin compound represented by the following 201219599 1), (B) a cationic amine ester resin emulsion, c)~ having an amine group selected from active hydrogen, an epoxy group , mercapto and mercaptopropene = one or more of the reactive functional groups in the oxy group, more than one diarrhea couple &d;D (D) organotitanium chelate compound, (E) tetravalent hunger compound, (F) _^ compound '(G) fluorine compound and (H) water; ,, here, the total solid content of the resin compound (A), the cationic amine ester resin emulsion (B) and the decane coupling agent (C) Solid component of {(As) + 曰D + (Cs) cationic amine ester resin emulsion (B) = (Min) by weight ratio [(Bs) / {(As) + (Bs) + (Cs)}] Calculated as 0.10~〇.3〇; and the solid content of the resin handle (A), cationic amine ester resin emulsion (b) Shixi burning coupler (C) {(As) + (Bs) + / Cs)}' The solid content of the decane coupling agent (C) (cs) is 0.60~〇·85 in terms of weight ratio [(Cs) (As) + (Bs) + (Cs)}]; relative to organic titanium Titanium equivalent amount (DTi) of the chelate compound (D) The solid content (Cs) of the oxime coupling agent (C) is 50 to 7 以 in weight ratio 丨(Cs)/(DTi)}; the amount of titanium relative to the organic titanium chelating compound (D) (DTi , the vanadium equivalent amount (Ev) of the compound (E) of the tetragen is 0.3 〇 to 〇.5 重量 in terms of a weight ratio ((Ev) / (DTi)); relative to the resin compound (A), a cationic amine The total solid content of the ester resin emulsion (b) and the sand-burning coupler (C) {(As) + (Bs) + (cs)}, and the amount of the molybdenum compound (F) in terms of molybdenum (Fm.) by weight ratio [(Fm.) / {(As) + (Bs) + (Cs)}] is calculated as 0.003 to 0.03; 15 201219599 4003 5pif with respect to the resin compound (A), the above cationic amine ester resin emulsion (B), and the above The total solid content of the decane coupling agent (C) is raj + (Bs) + (cs)}, and the fluorine content of the above fluorine compound (G) is a weight ratio [(Gf) / {(As) + (bs) + ( Cs)}] is calculated as 001 to 0.1; and 'pH is 4 to 5. Remember [Chemical 4]

OH

In the formula (I), the γ2 bonded to the benzene ring is independently a hydrogen atom, the fluorenyl group represented by the following formula (II) or the formula (ΙΠ), and the number of substitutions of the fluorenyl group per one benzene ring The average value is 〇2~丨〇. η represents an integer of 2 to 50. Here, the average value of the substitution number of the fluorenyl group means a value obtained by dividing the total thiol group-introduced number by the total benzene ring number (i.e., 2η). In the present invention, when the sulfhydryl group is selected as the oxime or oxime 2, the resin compound (a) has a cationic functional group having a primary amino group to a tertiary amino group and a quaternary ammonium salt group, and thus is object-oriented to the invention of 201219599. The surface treatment liquid which is acidic (the pH value is more stably dissolved. Further, in the present invention, 4 to 5) may be 2 to 50. When n is less than 2 faces, 'right η exceeds 50 丨 j. In addition, in the present invention, when the average polymerization degree η is set to 2, the corrosion resistance imparting effect is insufficient, and the other a is reduced in water solubility, thickening, and the like. In the treatment liquid, storage stability becomes insufficient. Stability is reduced, resulting in storage stability [Chemical 5] [Chem. 6]

Hg R4 A' In the formula (II) and the formula (III), ^, ^, ^, and ^, respectively, each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms. When the carbon number of the alkyl group or the hydroxyalkyl group exceeds 10, the resin compound (A) cannot be sufficiently dissolved in water, and it becomes unstable in the treatment liquid and cannot be applied. Specific examples of Ri, R2, R_3, &amp; and &amp; oxime, ethyl, propyl, butyl, hydroxyethyl, 2-hydroxypropyl, hydroxyisobutyl and the like. &quot; A- indicates a hydroxide ion or an acid ion. Specific examples of the acid ion can be exemplified by the acetate ion, the acidate ion, the citrate ion, and the like. The resin compound (A) represented by the formula (I) is a bisphenol-formaldehyde condensate, and the synthesis method thereof is not limited, and for example, furfural and an amine can be caused to act on bisphenol A in the presence of a base catalyst. obtain. The cationic amine ester resin emulsion (B) in the surface treatment liquid of the present invention has at least one cationic functional group selected from the group consisting of a primary amino group to a tertiary amino group and a quaternary ammonium salt group as a cationic functional group. The polyol, the isocyanate component, and the polymerization method which are constituent monomer components are not particularly limited. Examples of the cationic functional group include an amine group, a mercaptoamine group, an ethylamino group, a didecylamino group, a diethylamino group, a tridecylamino group, a triethyl group, and the like, as long as it is a primary amino group. The tertiary amino group or the fourth-order salt group is not particularly limited. The decane coupling agent (C) in the surface treatment liquid of the present invention is not particularly limited as long as it has at least one reactive functional group selected from the group consisting of an active hydrogen-containing amine group, an epoxy group, a fluorenyl group, and a methacryloxy group. One or more kinds of decane coupling agents are not particularly limited. Particularly preferred is a tri-oxygen group having three alkoxy groups. If a specific example is given, N-(aminoethyl)-3-aminopropyltrimethoxy decane, 3-aminopropyltrimethoxy decane, 3-glycidoxypropyltrimethyl can be used. Oxydecane, 3-glycidoxypropylmercaptodimethoxydecane, 2·(3 4_epoxycyclohexyl)ethyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, etc. . The organotitanium chelating compound (D) in the surface treatment liquid of the present invention may, for example, be titanium acetylacetonate, titanium octyl glycolate, titanium tetraacetate pyruvate or titanium ethyl acetate. Titanium nitrate, titanium sulfate, titanium acetate, titanium phosphate, 18 201219599 40035pif cannot be stably dissolved in the treatment liquid of the present invention, which is not preferable. Furthermore, the highly polar water which is affected by the addition of the complex compound is also beneficial to the tetravalent axis compound used in the surface treatment liquid. (8) The pentavalent antimony compound has high water solubility and is not used in the Ming Dynasty. </ br> (4) The compound (7) used in the surface treatment liquid may specifically include monomethane, monomethylate, sodium, 8% m, zinc citrate, etc. Molybdenum filling == In the present invention, 'better gamma machi wei: added a fluorine compound at the surface of the towel. Here, the type of the fluorine compound (6) is exemplified by hydrogen, acid hydrogen gas, hydrogen i boric acid, =, -, thief, and salts of these acids. The towel of the present invention is preferably one or more selected from the group consisting of these fluorine compounds. In the surface treatment liquid of the invention, it is necessary to calculate the solid content of the resin compound cationic urethane resin emulsion (B) and the decane coupling agent (c) 201219599 {(As) + (Bs) + (Cs)} The solid content (Bs) of the cation acetate emulsion (8) is set to be 〇1〇~ by /{(As) + (Bs) + (Cs)}. 3〇. When the above [(weight ratio) is less than 0.10, the ratio of the amine vinegar resin is too small, the heat retention property, and the storage stability of the surface treatment liquid are deteriorated. Another = resistance to contact If the above weight ratio exceeds 0, 30 (four) solution ship difference. More q = face,. Further, in the surface treatment liquid of the present invention, the total solid content of the compound (A), the cationic amine resin resin, and the resin (8) {(As) + and the Wei coupling agent ^-1 (C) ) (Cs) KAS) Hh (Bs) + (Cj}]tt^〇.6〇^〇85〇a;b[(Cs)/ ratio less than 0.60, solvent resistance is poor, if reset or surface treatment is described above _ stock = the amount of the material (9) in the surface treatment liquid of the present invention (DTi), the organic titanium compound component (cs) is set to be in a weight ratio of {70 1 (8) solids, if the above weight The coating property of the ratio exceeding 7^^^ or storage stability is lowered. It is preferable that the loze property of 55~^ becomes high, and after degreasing

= body::fΚί)=heavy/two: noodle wide coupling agent (.) hydrolyzed into money alcohol (= 7 base money (coffee (-ORW - agent dissolved in water heart == 20 201219599 4〇〇35pif due to hydrolysis The produced alcohol is volatilized in the treatment film of the present invention, and is used as an active ingredient to form a four-machine titanium chelate in a titanium equivalent amount (Dti) which is dried in the surface treatment liquid of the present invention. The amount of conversion (EV) is the weight ratio (E / = the ratio of the compound (8) if the above weight ratio is less than 0.3. Then the coating property after degreasing is decreased. It is preferably ^"^ & (4) In the surface treatment liquid, 'will be combined with the resin compound mrf vinegar resin (10) (b) and μ coupler (8) (1): it {{AS> + (Bs) + (Cs) 丨: (F = The amount of conversion (FmJ is set to 〇·003~〇·03 in terms of weight ratio [('ΜΑ) 2 S,]. If the weight ratio is less than a small amount, the resistance to black is difficult to be 'when the ratio of 4 is more than q Obtaining a storage stability of the surface treatment liquid, and obtaining a higher degree of blackening resistance, preferably 0.006 or more. In the surface treatment liquid of the present invention, the cation is relative to the resin compound (4) The amount of the above-mentioned fluorine compound (6) of the amine lyophile emulsion (B) and the above-mentioned Wei coupler (c) is set to an α weight ratio [(As) + (Bs) + (Cs) 丨] (Gf) / {(As) + (Bs) + (Cs)}] is calculated as 〇.〇ι~〇". If the above weight ratio is less than 0.01, the sweat resistance is poor, and if the above weight ratio exceeds 〇1, corrosion resistance cannot be obtained. And the storage stability of the surface treatment liquid. In order to obtain a higher degree of sweat resistance, it is preferably 0.07 or less. The surface treatment liquid of the present invention has a pH of 4 to 5. If the pH value 21 201219599 is less than 4 ' Since the surface of the surface of the zinc-zinc steel plate is dissolved, the resistance of the film is reduced. On the other hand, if the pH exceeds 5, the stability of the surface treatment liquid cannot be obtained. Here, the pH is adjusted to 4~ The acidic agent used at the time of 5 is preferably 酉夂g g, formic acid, hydrofluoric acid, fluoride, etc., and the strong acid such as sulfuric acid or nitric acid is poor. The reason is that if sulfuric acid or nitric acid is used, it can be seen at pH value. During the adjustment, the cationic age or cationic amine vinegar becomes gelatinous in the surface treatment solution due to pH shock (local and rapid pH change). In addition, the salt formed therewith has a high elution property, and the corrosion resistance is lowered. Acetic acid and formic acid are suitable for adjusting the pH because they are weak acids. Further, the acids are highly volatile because of the chemistry of the present invention. It is volatilized during drying, and there is little residual in the film. Therefore, even if it is excessively added, the performance is less, and it is preferable in this respect. On the other hand, when the value of 1311 becomes too low, the pH is adjusted to 4 The alkaline agent to be used is preferably ammonia or an amine having a point of 1 〇〇 ° C or less. In addition, when a strong alkaline agent such as Na0H or K〇H is used, a gelation may be generated in the same manner as in the case of a strong acid agent, and NaOH or KOH or the like may be used. The water (Η) used in the present invention is preferably a resin compound (A), a cationic amine ester resin emulsion (B), a decane coupling agent (c), an organic titanium chelating compound (D), and the like. The effect of the acid component or the alkali component at the pH adjustment is small. For example, a hardness-increasing component such as Mg, ca, or Si contained in water as an impurity may lower the solubility or dispersibility of the resin compound (A) or the cationic amine Sa resin emulsion (B) of the present invention, resulting in generation of these. The condensate of matter is not good. 22 201219599 *+uujjpif When Na or Cl or the like contained in water as an impurity remains in the film, the enthalpy may be lowered or the coating adhesion may be made. Therefore, the produced water (5) It is preferable that the amount of impurities is small = small, please be better than the piano cm, and = 10 gS/cm or less. Further, the solid content concentration of the surface treatment liquid of the present invention is preferably 4 wt% to 20 wt% based on the solid content concentration at the time of drying for 2 hours. The reason for this is that if the concentration of the (IV) body component is in the range of 4 wt% to 20 wt/〇, the adhesion amount of the surface treatment film to be described later is easily ensured, and the storage stability of the surface treatment liquid is also excellent. The basic components of the surface treatment liquid of the present invention have been described above. However, in the present invention, the following components may be further contained as needed. That is, in the present invention, wax can be contained in the surface treatment liquid to ensure the lubricity of the film. The cerium (W) is preferably formulated in such a manner that the solid content (Ws) of the wax is a total of the solid content of the resin compound (A) and the cationic urethane emulsified emulsion (B) {(As) + The weight ratio of (Bs)} is [(Ws) / {(As) + (Bs)}], which becomes 〇·2~〇4. When the content is 0.2 or more, the desired lubricity can be obtained. On the other hand, when the content is 0.4 or less, lubricity can be ensured, and it is economically advantageous, and the corrosion resistance is not lowered. good. More preferably 〇3 to 0.4. The wax (w) used in the present invention is preferably at least one selected from the group consisting of waxes having a melting point of 7 &&gt; c 120 ° C, and specific examples thereof include polyethyl hydrazine wax, 23 201219599 4UUJ3pif oxidized polyethylene.躐, material job, micro crystal money n point is 7 (r or more to obtain the required lubricity, if the melting point is set to 120 or less, a hard film can be obtained, and the required lubricity can be obtained. Preferably, the 蠛(w) is a ritual liquid which is stably dispersed in water by an emulsifier, and preferably has a particle size of 0.08 μm to 〇3 μιη. If the particle size is 〇〇8 or more, the desired granule is obtained. The effect of the lubricity does not increase the amount of the emulsifier used, so the alkali resistance or the coating property does not decrease. On the other hand, if the particle diameter is set to 0.3 μm or less, it does not occur. Further, in the surface treatment liquid of the present invention, a water-repellent or a rhubarb-enhancing agent may be added as needed in the treatment liquid, which is low in specific gravity, and which is excellent in storage stability. The type of the antifoaming agent is not particularly limited, and for example, polyfluorene or fatty acid can be used. The so-called wetness-improving agent is a water-soluble solvent such as ethanol, which is used to reduce the surface tension of the surface treatment liquid, to improve the full wettability of the galvanized steel sheet, and to improve the uniformity of appearance. In addition, the T-butanol and the butyl cellosolve are not limited to these solvents, and the dextrin enhancer containing the block B also has a four-bubble effect, and is suitable for the surface treatment liquid of the present invention. Nitrate such as nickel nitrate or ammonium nitrate may be added to further increase the blackening resistance. As described above, nitric acid may cause a pH shock, but if it is a nitrate, it does not have a pH impact. t Then, the above surface treatment liquid is used. The method for producing a plated steel sheet and the plated steel sheet obtained by the production method will be described. 'When the surface treatment liquid of the present invention is used to form a surface household 24 201219599 on the plated steel sheet, it is necessary to reach It. Apply the surface treatment liquid to the keying steel plate to reach the plate 4 5Gt: ~18 (the rc is dried to form the adhesion amount per 面9 /, and the 仃 is missing on the surface of the _ plate, „ 4 gm 2 surface treatment film. g/ In the case of m2, the adhesion amount per one side of the two treatment films is less than the resistance of the 〇·2 film, and on the other hand, if the surface treatment and the adhesion amount of the imperfect I- exceed the U coffee 2, the adhesion is adhered. The effect of the amount of saturated surface is unfavorable and the coating property is lowered. Therefore, the attached one of each single is 。. . . 2 — Η 8 coffee 2, more than 2 to Mg/m 2 , more preferably 0.4 g. /m2 to 14g/m2. 2 The square coating machine (the three-parent method, the two-roll method, etc.) which applies the surface treatment liquid of this invention on the plated steel plate, and the extrusion coating extrusion machine Any of the previously known methods. Alternatively, the coating amount may be adjusted by a knife method or an I-can press method after the coating treatment, the silk treatment, or the blast treatment using the cloth scale, and the appearance uniformity and film thickness may be performed. Homogenization. The surface treatment liquid of the present invention is coated on the steel sheet - preferably, it is dried without being washed with water. Dry (four) structure can be used, human fan, hot air furnace, high frequency induction heating furnace, infrared furnace and so on. The drying as described above is to adjust the plate temperature of the plated steel sheet itself to 5 〇t~ song. of_. If the plate temperature is less than 5 叱, the U-water knives in the film become insufficient. On the other hand, the arrival of the board temperature exceeds C, the wealth is only uneconomical and the new one becomes hard and brittle, and the profitability of the processing department declines. The present invention having the surface-treated film formed by the above method 25 201219599 40035 pif === can be applied to the surface of the resin film to obtain a higher film-forming surface-treated skin test surface. The role is explained. It is presumed that the components of the watch of the present invention have the following effects, but the present invention is not subject to such refinement == resin compound (α), cationic fine 3 read (8), and Wei coupler (C) in the treatment liquid. For the domain, the skeleton of the film is formed by some main components. s ΟΛ Adjusting the pH value of the surface treatment liquid containing a cationic functional group (the above-mentioned general formula (ΙΙ) or the general-purpose resin compound (α) to (3) the surface treatment liquid increases stability to ensure storage stability. 'By giving a cationic property, a resin compound (Α)* is dissolved in a test solution: to form a film having alkali resistance. Further, by selecting bisphenol as a skeleton of a tree-like substance (Α), In addition, it is difficult to dissolve in a polar solvent (enhancement of solvent resistance), and adhesion and corrosion resistance are improved. However, the above-mentioned resin compound (Α) is liable to have a yellow color (resistance, yellowing decrease) due to heating and is easy to become Therefore, in the present invention, the cationic amine ester resin emulsion is blended to alleviate the hardness of the phenol resin, and the corrosion resistance of the processed portion is ensured. The cationic amine ester resin emulsion (Β) has the above effects, but On the other hand, the film is easily peeled off from the polar solvent. Therefore, in the present invention, it is intended to ensure solvent resistance (yield to a polar solvent) and yellowing resistance, and 26 201219599 .li己石夕烧 coupling agent (c). Shixi sinter coupling agent (c) due to the hydrolysis of the alkoxy group at the end to form an active (4) anthracyl group (Si 〇H), thus contributing to the raw material (mineral zinc layer) or overcoating Further, the adhesion of the coating film (tGpeGating) is improved. Further, a part of the sulphur coupling agent (C) is dehydrated and condensed to produce a sulphur-oxygen bond (SMD-Si), which is continuously polymerized (polymerized). Oxyalkylation: Si Ο Si O-Si-). This results in an extremely stable structure, which imparts corrosion resistance, solvent resistance, and yellowing resistance to the film. Therefore, it can be considered as 'by using it in an appropriate ratio as a surface. The resin compound (A), the heterozygous fine emulsion (8), and the Shixia coupling agent (C)' which are the main components of the treatment liquid can obtain various properties in a good balance. However, in the case where only the above domains are used, It is impossible to obtain a solution to the problem of the previous problem and the blackening phenomenon. Therefore, in addition to the above-mentioned domain division, the chemical titanium solution has an organic titanium chelate compound (9) as an essential component. (D) When the film is formed into a film, it is used as a promoter for oxygen burning. Catalyst == and =: _ fly _ silly 07 Eclipse "birth and resistance" gluten or coating properties are also improved. In order to get, the effect 'as mentioned above, according to the Wei coupling agent () 1 When the predetermined amount of the organotitanium chelate compound is determined to be small, the desired effect cannot be obtained, and the hard and brittle skin becomes: ::=== =, which is caused by the organotitanium S compound (D) The scent of oxygen is promoted, but since the surface treatment liquid "suddenly promotes the heat of the stone, it is burned, so when the content is excessive, the storage stability 201219599 40035pif ==: inhibition of the inhibition) declines, after storage Unable to get and save before

The surface treatment liquid of the present invention allows the tetravalent hunger compound (E) to be an essential component. It is presumed that in the present invention, an inhibitor of tetravalent compound (8) etch (for example, passivation of zinc) functions. In particular, it is difficult to dissolve in the wet environment, and it is difficult to dissolve in the wet environment, and it is presumed that even in the case of plating =, the force is as strong as the work, and the surface treatment film or the fiber J is resistant to damage: : Shape 3: The surface of the part of the anti-aliasing or the cationic functional group of the cationic functional group is the same as the same as the material of the county (four) ^ ^ ^ and the surface treatment liquid as the invention will also (10) Compound (F): _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Oxygen is deprived, and oxygen is not fully supplied. (4) is anoxic (tetra) zinc oxide. 28 201219599 40035pif Oxidation of oxygen type appears black. In the present invention, by introducing a molybdic acid compound Excellent blackening resistance can be obtained in the surface-treated film because molybdenum is a transition metal, and oxides of Mo〇2 and M0O3 are bonded to oxygen. Further, molybdenum bonded with oxygen is also present. Acid (ΜοΟ/-). Therefore, it can be considered that in the present invention, molybdenum S^(M A part of o〇4) is converted into _oxide (Mo03, etc.) under the conditions of high temperature and humidity or in a corrosive environment, thereby appropriately supplying oxygen to the surface of the zinc recording, so that it is difficult to form anoxic zinc oxide. It is presumed that a surface treatment film for suppressing blackening is obtained by such a mechanism. In the compound liquid, the heavy shirt is fluorinated and = because: it can be excellent by adding a fluorine compound (G). In the case where the person touches the zinc-steel plate, the human sweat adheres to the plate, and the portion becomes black^micro-hybrid over time. It can be considered that the viscous surface of the galvanized surface is lightly weakly oxidized. The base point of the ship, the second is the sweat of the person (weakly acidic), and it seems to be slowly growing on the surface of the galvanized electrode. The effect of the addition is that the surface inventors speculated that the zinc surface of the fluorine compound (6) formed Zn, When the surface of the A1 plate is in contact, at the time of plating, the hydrofluoric acid which is easy to generate F ions is good. The salt or the salt thereof has a large effect of improving the sweat resistance: the surface layer is stable, so that the soluble compound can be suppressed when the human touches, and plating is performed. The application is compared with the example 29 201219599. Table 1 (Table la and Table lb) The resin compound (a) shown, the cationic amine ester resin emulsion (B) shown in Table 2, the decane coupling agent (C) shown in Table 3, the titanium compound (D) shown in Table 4, and Table 5 are shown. The hunger compound (E), the acid-reducing compound (F) shown in Table 6, the fluorine compound (G) shown in Table 7, and the W (W) emulsion shown in Table 8 were appropriately mixed to prepare a surface treatment liquid. The hot-dip galvanized steel sheet shown in Table 9 was used as the processing original sheet. For example, the surface treatment liquid of the example was prepared so as to have the composition of Table 1〇&gt;4 to Table 121, and was adjusted to the following table using acetic acid and ammonia. 2 to the enthalpy values shown in Table 12-2, the preparation was carried out using deionized water so that the solid content concentration at 11 hours after TC drying for 2 hours was 10% by weight. 1 In other surface treatment liquids, acetic acid is used as an acidic component, ammonia is used as an alkaline component to adjust the pH value, and solid components are produced. The above deionized water is made of conductivity W. On the surface, the wire was heated so as not to be washed with water to reach the plate temperature as shown in Table 13, and a steel plate was produced. The surface treatment film is prepared and treated with a skin flag (light downforce, rotation speed; the amount is applied by coating 13 degrees #). In addition, the amount of adhesion is determined by the amount of adhesion of the Si to the reactor of the decane coupling agent (C). The amount of Ding, converted from S1 to the skin 30 201219599t The quality of the surface treatment liquid and the galvanized steel plate produced (planar impurity, bending plus: ^ part of the secret, after the degreasing _ sex, black resistance Each test of the properties of the property, the color changeability, the applicability, the applicability after degreasing, the solvent resistance, the storage stability, the sweat resistance, and the lubricity were shown in Table 14. Furthermore, the evaluation of the quality performance was carried out under the following conditions. (1) Resistant to the flat portion Each sample was subjected to a salt spray test (JIS-Z-2371-2000), and the area ratio of white rust after 120 hours was evaluated. The evaluation criteria are as follows: ◎: The area ratio of white rust generation is 〇%. 〇+: The area ratio of chalk production is less than 5〇/〇〇: the area ratio of white rust is 5% or more and less than 1〇% 〇-: The area ratio of white rust is more than 1%, less than 2〇% △: White The area ratio of rust generation is 2% or more and less than 4% by weight. X: The area ratio of white rust generation is 4% or more. (2) Resistance to insects in the bent portion. Each sample is sandwiched between rods having a diameter of 2 ( It is not bent by iron steel 180. It is tightened with tiger sweet. The curved sample is subjected to a fog test (JIS-Z-2371-2000) to pass the white rust on the outer side of the curved portion after 72 hours. The area ratio is evaluated as follows. ◎. The white area of the bent portion is 〇0/〇〇+: the area ratio of white rust in the bent portion is less than 5% 〇··White rust in the bent portion The area ratio is 5% or more and less than 1 〇〇/〇: the area ratio of white rust generated in the bent portion is 1% or more, and 'less than 40%'. 31 201219599 _____Γιι △: Area ratio of white rust in the bent portion 40% or more and less than 80% X: The area ratio of white rust in the bent portion is 8〇% or more. (3) The button resistance after degreasing is tested as a degreaser CL-N3 64S (manufactured by Parkerizing Co., Ltd.) Dissolved in pure water at a concentration of 20 g/L, and heated to 6 ° C. Each sample was immersed in the alkali solution for 2 minutes, taken out, washed with water, and dried. Each sample was subjected to a salt spray test (JIS-Z-2371-2000), and the area ratio of white rust generation after 72 hours was evaluated. The evaluation criteria are as shown in the above evaluation (()) Each sample was allowed to stand in a constant temperature and humidity machine controlled to a temperature of 80 ° C and a relative humidity of 95% for 24 hours, at which time the brightness (l value) was changed (AL = L value after the test before the test) The evaluation criteria are as follows. The L value is measured using the SR2 制造 manufactured by Nippon Denshoku Industries Co., Ltd., and the Specular Component Excluded (SCE) mode (removing the specular reflected light). L〇^AL&lt;-6 Δ : -14^AL&lt;-10 x : AL&lt;-14 (5) Heat discoloration resistance Each sample was heated in an infrared induction furnace for 3 sec to a plate temperature of 500 c 'Keep 3 After 〇 seconds, visually observe the surface appearance of 32 201219599 40035pif when it is naturally cooled to room temperature. ◎: No color change 〇: very pale brown △: light brown X: brown (6) coatability Delicon (registered trademark) #700 as a melamine alkyd paint for each sample was applied. (Manufactured by Dainippon Coatings Co., Ltd.) 'At 13 〇. (: After calcination for 30 minutes, a film having a film thickness of 30 μm is formed, and then immersed in boiling water for 2 hours, and immediately into the square (1 〇 Cut marks of X10 '1 mm intervals' of steel green body. Furthermore, the Erichsen extruder was used to carry out a 5 mm extrusion process so that the cut portion was on the outer side, and the tape was peeled and peeled off, and the peeling area of the coating film was measured. The benchmark for the evaluation is as follows. Further, the Erichsen extrusion condition was set to a punch diameter of 20 mm, a die diameter of 27 mm, and a press width of 27 mm in accordance with JIS-Z-2247-2006. ◎: not peeled: the peeling area is less than 3% 0: the peeling area is 3% or more and less than 1 〇〇/0: the peeling area is 10% or more and less than 2 〇〇/0 Δ: the peeling area is 20% or more and less than 50 % x : 50% or more of the peeling area (7) The coating property after alkali degreasing was subjected to the same alkali degreasing as in the above (3), and the same coating property test as in the above (6) was carried out on each of the samples. The evaluation criteria are also the same as (4) above. 33 201219599 4UU35pif (8) Solvent resistance A load of 4 was applied to a gauze impregnated with methanol and pressed against the surface of each sample to rub N (5 〇〇 gf). The friction marks were evaluated visually. Evaluation standard ^Main return 10 times ◎: No trace. see. Μ: No traces can be seen from the observation of the upper part, but a slight permission is observed when tilting. 〇: No traces are observed when viewed from above, but it is noticeable when obliquely observed. - A slight permission is observed when viewed from above. △. The crane has visible marks when viewed from above. x: peeling of the film. (9) Storage stability 30. The surface treatment liquids which were not used were stored in a temperature bath of 4 ° C. The evaluation of the surface treatment liquid was carried out to evaluate the appearance of each surface treatment liquid. ◎: No change 〇. A very small amount of precipitate is visible △. A slight amount of smear is observed or the viscosity is slightly higher x: a large amount of (4), or gelation (10) sweat resistance is added to the surface of each sample according to JIS Artificial sweat of B7001 -1995 10 := The rubber stopper of the f is pressed against the dropping part to make a part of the human/f heart of the certain area. The test piece is controlled to a temperature of 40 ° C, relative to 34 201219599 "humidity 80 After standing for 4 hours in a constant temperature and humidity machine of % environment, the appearance change of the area contaminated by artificial sweat was evaluated. The evaluation criteria are as follows: ' ◎ • No discoloration 〇: There is a slight discoloration △: slightly blackening x: obvious Blackening (u) Lubricity A disc-shaped test piece with a diameter of 100 mm was cut out from each sample to the punch diameter - such as surface ~ mold diameter: ^ other surface ~ blanking force (9) her ^ this pressure) ^^ t ( The conditions of the ton) were formed into a cup shape. The appearance of the molded product on the side of the extruded surface (outside of the side of the cup) was visually observed, and the degree of damage and the degree of blackening were evaluated. The evaluation criteria were as follows: ◎: The entire surface was hardly Change, uniform appearance 〇+ : Very slightly blackened, but the appearance is even 〇: slightly Damage and blackening have occurred, and the appearance is obviously uneven. :: Local damage and blackening occur, and the appearance is obviously uneven. △: Damage and blackening are caused violently with the corners as the center. x: Cannot be formed and damaged. 35 201219599 4UUJ3pif [Table la] Table la nucleolipid compound (A) Y1 Y2 No. Z group: Formula (II) z group: General formula (II) Average value of substitution number of Z group η R1 R2 R1 R2 A1 Hydrogen hydrazine group Ethyl 0.4 5 A2 ethyl methylhydropropyl 0.7 3 A3 ethyl propyl hydrogen ethyl 0.4 10 A4 hydroxyethyl hydroxyethyl hydroxyethyl hydroxyethyl 0.5 5 A5 -Ci2H23 methyl hydrogen argon 0.5 5 A6 - C12H22OH Methylhydrogen hydride 0.5 5 A7 Hydrogen hydrazinoethyl 0.1 5 A8 Hydrogen hydrazinoethyl 1.2 5 A9 Hydrogen hydrogen methylethyl 0.4 80 * The group represented by ϋ i (π) is used as the Z group. [Table lb] Table lb Resin Compound (A)

No. Y1 Y2 The average value of the substitution number of the Z group η z group: General formula (III) Z group: General formula (III) R3 R4 R5 R3 R4 R5 A10 Hydrogen hydrogen methyl methyl ethyl methyl 0.4 5 All B Methylhydrohydrin propyl hydrogen 0.7 3 A12 ethyl propyl methylhydroethyl methyl 0.4 10 A13 hydroxyethyl hydroxyethyl hydrogen hydroxyethyl hydroxyethyl hydrogen 0.5 5 A14 -C12H23 methyl hydrogen hydride 0.5 5 A15 -C12H220H methyl hydrogen hydride hydrogen 0.5 5 A16 hydroxyethyl hydroxyethyl hydrogen hydroxyethyl hydroxyethyl hydrogen 0.1 5 A17 hydroxyethyl hydroxyethyl hydrogen hydroxyethyl hydroxyethyl hydrogen 1.2 5 A18 hydroxy Hydroxyethylhydrohydroxyethylethylhydroxyethylhydrogen 0.5 70 * The group represented by the formula (II) is used as the Z group. 36 201219599t [Table 2] Table 2 Amine ester resin (B)

No. Amine ester resin (B) Ionic manufacturer B1 7 Yin Li show V y Xiyi HUX-670 Cationic ADEKA (share) B2 Superflex 600 Cationic first industrial pharmaceutical (share) B3 UC-20 Cationic Sanyo Chemical Industry Co., Ltd. B4 Adeka Bontiter UX-206 Nonionic ADEKA (Shares) B5 Hydran AP-10 Anionic DIC (Shares) [Table 3] Table 3 Decane Coupler (C)

No. decane coupling agent (c) Cl 3-mercaptopropyltrimethoxy oxalate C2 N-(2-aminoethyl)-3-aminopropyltrimethoxydecane C3 3-epoxypropoxy Propyl trimethoxydecane C4 3-mercapto propylene methoxy propyl trimethoxy oxalate C5 vinyl trimethoxy oxetane [Table 4] Table 4 Titanium compound (D)

No. Titanium compound (D) D1 Titanium acetylacetonate (Ti: 12_5 wt%) D2 Titanium tetraacetate pyruvate (Ti: 10.8 wt%) D3 Titanium nitrate (Ti: 16.2 wt%) D4 Fluorotitanic acid ((Ti : 29.2 wt%)) [Table 5] Table 5 Vanadium Compound (E)

No. Vanadium compound (E) El oxalate oxalate (V: 32_9wt%) E2 Vanadium acetonate pyruvate (V: 19_2wt%) E3 Vanadium sulfate (V: 31.2wt%) E4 Metavanadate (V: 43.5wt%) 37 201219599 40U35pif [Table 6] Table 6 Molybdic acid compound (F) No. Molybdic acid compound (F) F1 Na2Mo04-2H?〇F2 (NH4)6M〇7〇24*4HoO F3 (ΝΗ4)3[ΡΜο1204η1·3Η, 0 [Table 7] Table 7 Fluorine Compound (G) No. Fluorine Compound (G) G1 Hydrofluoric Acid G2 Hydrofluoric Acid G3 Hydrofluorotitanate G4 Acidic Ammonium Fluoride G5 Sodium Fluoride [Table 8] Table 8 Wax (Table 8) W) lotion

No. Wax type (W) Melting point (°c) Solid content of the dispersion (wt%) Particle size (μηι) W1 Oxidized polyethylene wax 115 20 0.1 W2 Microcrystalline wax 90 20 0.1 W3 Paraffin 50 20 0.1 ※Used to emulsify A product obtained by forcibly kneading the wax described above. [Table 9] Table 9 Galvanized steel sheet No. Treatment of original plate C plated steel plate) Plating adhesion amount GF1 炫融录Ζη·5·0 mas% A1-0.6 mass% Mg-0.04 mass% Ni alloy steel plate 90 g/ M2 GF2 Hyun fusion bond Ζη-4·5 mas% Al-0.8 mass% Mg-0_03 mass% Ni alloy steel plate 60 g/m2 GF3 炫融办Zn-5.1 mas% Α1-0·9 mass% Mg-0.09 mass% Ni alloy indium plate 90 g/m2 GF4 炫融ΖΖη-5·0 mas% Al-0.5 mass% Mg alloy steel plate 90 g/m2 GF5 melt bond Zn-5.1 mas% A1 alloy steel plate 90 g/m2 ※ plating is It is carried out on both sides, but the above indicates the amount of plating adhesion per one side. 38 201219599 【1-01&lt;】Ji-so inchΙ-0Ι&lt;(W) Solid content 〇ooo Ο ο o ο ο ο ο Ο 〇oo Ο o ο 〇〇&lt; 1 1 1 1 1 1 1 1 III 1 1 1 1 1 1 I o ^ Η i 5? 寸 inch inch inch inch inch inch inch inch inch inch inch inch inch inch type inch&lt; inch 0 3 inch ϋ inch inch inch inch inch inch inch inch inch δ inch inch inch inch s inch inch寸α inchϋ. inchο inchϋ /-N SX Mo conversion VO dov〇Ο ο VO ο ν〇ο VO ο ν〇Ο ν〇Ο ο ν〇ο Ο VO o VO ο v〇Ο V〇dv〇Ο 〇Ο〇Ο CS Uh fS ϋ. S &lt;Ν Ρη (Ν pu, fS tL. &lt;s CS [X. (Ν UU (S IJh (Ν ti, (N (Ν CN cs Uh CN &lt;Ν /^ N ω Vw/ V conversion inch d ο inch Ο inch ο inch Ο inch d inch ο inch ο inch ο 寸 inch Ο o inch d inch 寸 inch d inch Ο inch Ο type &lt; W »—i ω ω « W ω ω ω ««Η ω 1 SI 1 ω &lt;N w ΓΛ W CN ω (Ν ω /-NQS—✓ Ti conversion % F·^ τ-Η ί*Η 1.134 1.134 •H type inch&lt; Η QQ production Η QQ Ο tM Q ψ—^ QS inch QQQ inch Q inch Q inch QQ cs QQ inch Q »—Η Q /—N u ___- Solid content § S s § 00 «ο o in »r&gt; § SSS VO U-ϊ VO δ s § S Type m &lt; U u FH u * *&quot;Η u *-Η υ »TMH »&quot;Η υ »«Η Ο »-Η υ U C2 : C3 =1 : 1 GUG Ο 0Q V—X Solid content % S o Os VC CS iT) ... CN 〇\ cs Ό v〇o \〇iS σ\ (N CQ PQ CQ PQ ί*Η £Ώ ffl PQ PQ *-Η CQ PQ CQ CQ Ξ *-H »-H CQ CQ CQ /&quot;N c Vw / solid content % inch O inch ο 1Γ» dd inch inch Os CN (N inch inch inch &lt;&lt;&lt; CC &lt; TH c ^Η C &lt; τ*Η C &lt;&lt;&lt;&lt;&lt;c&lt; F*H &lt;&lt;&gt; Inventive Example 1 Inventive Example 2 | Inventive Example 3 I Comparative Example i Inventive Example 4 Inventive Example 5 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Inventive Example 6 Inventive Example 7 Inventive Example 8 Inventive Example 9 z CN m Inch 00 Q\ ο F1^ CN CO 2 in v〇卜00 201219599

Jass? 〇ο Ο 〇〇〇o 〇〇ooo ο ο t 1 1 1 1 1 1 1 1 1 1 1 1 I inch ^r inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch寸 inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece case CN Uh cs Cl. cs Uu CN [X. (N tin (N Ph (N Ph cs tu&lt; CN P-. CN ϋΗ (Ν Ρη CO 〇0-34 | 1 0.44 1 I 0.48 I 0.32 0.35 1 0.46 1 in 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ω fS ω 1 〇·75 1 | 0.85 | CN oo o 0.88 yr\ 卜.25 1 V-H - 〇II t QQQQQQQQQPQQQQ (N 00 v〇&lt;N ssss § S s S § υ u U uuu FH u U o υ Os 〇\ r«H ov〇v〇VO V〇VO v〇ν〇ν〇ffl »&quot;H ffl PQ ffl PQ (Ώ m OQ PQ «—m CQ CQ PQ CQ ω Os &lt;N inch inch inch Inch inch CCC c C &lt; r«H c C &lt;&lt;&lt;&lt;&lt; Comparative Example 10 Inventive Example 10 | Inventive Example ii | Comparative Example 11 | Comparative Example 12 1 Inventive Example 12 I Inventive Example 13 Comparative Example 13 Comparative Example 14 Inventive Example 14 1 Inventive Example 15 Comparative Example 15 1 Inventive Example 16 1 Comparative Example 16 σ\ ΓΛ (N iQ v〇(N oo (N a (Ν ΓΟ Ί Ί 'ϊινιί : (ΛΟ·蓉伞^灭: (ο) -^^JJSS now: ur#&lt;nJJ*T-冢sl&gt; s : (Η) *#&lt;1π^^ί»^€^:(α) 二#&lt;0筚域:(3) *Zhao Youhui Raspberry Iss&ti furfural: (a)-rong Umbrella ^铛 rate "祓驷衾驷你&lt;: (V) 201219599 J-CLlrlso inch si (X7) ο ο ο o ο oo Ο ο ο ο ο Ο ο 〇〇〇〇 〇〇〇〇 〇〇〇〇 (X6) 0.050 0.050 0.050 0.050 0.050 0.050 0.049 0.050 0.050 0.050 0.050 0.040 0.040 0.050 0.050 0.050 0.050 0.048 0.048 0.048 0.048 0.048 0.050 (X5) @000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.000.00 0.006 0.0060.000.000.000.00 0.007 0.007 0.007 0.007 0.007 (X4) 0.40 0.40 0.40 0.40 0.40 0.40 I 0.40 0.40 0.40 0.00 0.40 0.00 0.00 0.40 0.40 0.40 0.40 0.36 0.40 0.40 0.40 0.40 0.40 (X3) § s 〇〇in § § 卜(X2) 0.75 0.75 0.75 0.75 0.73 0.70 0.68 0.75 0.75 0.75 0.75 0.65 0.65 0.25 0.75 0.75 0.75 0.72 0.54 0.63 0.82 0.87 0.75 (XI) 0.20 0.13 0.11 0.08 0.27 0.29 0.32 j 0.20 0.20 0.20 0.20 0.06 0.06 0.50 0.20 0.20 丨0.20 1 —_ ! 0.23 0.23 0.23 0.13 0.12 0.20 pH — — inch — — inch — — — — — — inch — — — — inch ' — — wt% mm ro m ro cn fO ο ο VO mm CO ΓΛ ΓΠ m Pro-phosphoryl orthophosphate-phosphoric acid phosphatase phosphatase phosphatase phosphatase phosphatase phosphatase phosphatase phosphatase phosphatase phosphatase phosphatase phosphatase 2 Inventive Example 3 Comparative Example 1 Inventive Example 4 j Inventive Example 5 j | Comparative Example 2 1 Comparative Example 31 1 Comparative Example 4 Comparative Example 5 1 Comparative Example 61 Comparative Example 7 Comparative Example 8 1 Comparative Example 9 Inventive Example 6 Inventive Example 7 Inventive Example 8 Inventive Example 9 Comparative Example 10 Inventive Example 10 Inventive Example 11 Comparative Example 11 23 Comparative Example 12 No. CN m Inch 00 σ\ ο CN cn 1〇VO 〇〇〇\ ψ—4 2012 19599 J-asso 寸ooo 〇ooo ο o 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.000 0.000 0.40 0.40 0.24 0.33 0.49 0.55 0.40 0.40 00 ss 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.20 | 0.20 | 0.20 0.20 0.20 0.20 0.20 0.20 0.20 - inch * inch * - m inch * mmmmm cn orthophosphoric acid | orthophosphoric acid | | orthophosphoric acid | pro-phosphoric acid phosphoric acid; orthophosphoric acid | Inventive Example 12 Comparative Example 13 Comparative Example 14 Inventive Example 14 Inventive Example 15 Comparative Example 15 | Inventive Example 16 1 Comparative Example 16 ΙΟ fS VO 00 (N a (N m (m+ &lt;c) / ΟΜ) = /.χΑυ+®+ &lt;) / ("o) =9x*(u+PQ+&lt;&lt;) / rsd) &quot;sx - (ρα) / (&gt;3)=々x * (ρα) / (u) =£ x * (o+m+v) / (u) =3⁄4 &lt; (u+m+v) / ca) =ιχ (※) 201219599 J-asso inch 'li (w) solid content 4-> 〇 o ο Ο o ο ο ο Ο Ο OO 〆Ο w-ΐ Ο ο o Ο o Ο 00 1 1 1 I 1 1 1 IIII (N cn I 1 1 1 1 I o S—✓ Progressive Pu, Γ % Inch FH 〇 Ο 寸 inch inch inch寸 inch inch inch inch&lt; inch inch alpha inch Ο δ δ δ α Ο &lt;Ν α m ϋ Ο δ ϋ 〇 inch ϋ inch Ο δ inch ϋ inch Ο δ δ /—N Uh Mo %V〇CN VO ο ο O v〇〇ν〇Ο ν〇Ο ο ο ν〇Ο ν£&gt; Ο d ν〇ο ο ν〇ο ν〇ο VO dd ν〇dd ο 乡s 'TV ^WS 1 S &lt;Ν S 1 CS PLh CS Ρη (N &lt;N IX. fN Ρη £ ^Η Ε E Ε /^N w Vw^ V conversion inch d inch d inch d inch ο inch ο inch inch inch inch inch inch inch inch inch inch inch Inch d inch ο inch ο inch Ο inch ο inch o inch d inch d d d inch Ο #观iTt &lt; (NW (N ω &lt;Ν ω CN W (N m &lt;N ω CN ω CN W CN ω fN W (Ν ω &lt;N w &lt;Ν W CN W (Ν W »—Η ω ^H w *-H ω τ«Η ω T—H w ω /^NQ s—/ Ti conversion 1 **&quot; Η rH »-Η ^-Η fH Type inch&lt; QQQQQ y-^ QQQQ Η QQQQ Ω Q ^•Η QQQQQQ /-N u Vw/ Solid component ss S § ss § δ § SS s % SSS ss 8 s § Type m «—H u ^-H υ TH u T*H u υ »-Η υ 1~Η υ υ Ο rH Ο »~Η ϋ ^- Η υ f—Η υ uuo FH u rH υ /&quot;N CQ Solid content% V〇VO »—H ν〇Ό ν〇ν〇ν〇V〇ν〇ν〇ν〇VO 乡骚CN m ψ^ * ffl PQ FH PQ OQ PQ (Ώ PQ *—Η ffl F&quot;H PQ m CQ »—Η CQ m CQ m »*·Η CQ W PQ CQ /&quot;NC Solid component volume inch inch inch inch inch inch inch inch inch inch inch inch C-type &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; C &lt; C &lt; C &lt; C &lt; C &gt; C &gt; WORKING EXAMPLE 17 Inventive Example 18 Comparative Example 19 Inventive Example 19 Comparative Example 20 Inventive Example 20 Inventive Example 21 1 Inventive Example 22 1 Inventive Example 23 Inventive Example 24 Inventive Example 25 Inventive Example 26 Inventive Example 27 Comparative Example 21 Comparative Example 22 Inventive Example 28 Inventive Example 29 Comparative Example 23 Comparative Example 24 2 cn m in ΓΛ v〇m P; 00 m ΟΝ CO Ο inch 5 a; »〇CN »Τϊ m ε inch 201219599 JUSS0 inch 〇oooooo ο Ο Ο•fat lotion, (c ): decane coupling agent, 1 t 1 1 &lt; 1 1 &lt; I 1 inch inch inch inch inch inch inch inch 〇〇o 〇a 〇Ο a Ο ν〇Ο VO d vo o VO dv〇oo vo c5 &lt;3 d ν〇ο VO ο EE: iZ ε ίΖ inch inch inch o inch o inch o inch inch inch o inch o pair ο inch ο inch ο w Ξ Ξ w Ξ Ξ Ξ w ω Ξ fH *«h QQQQDQQQ t—Η Q t··^ Q ssss § ss S δ δ uuu ^H uouu υ υ 宝 1 1 JM m 密 PQ V—/ VO VO VO v£J ν〇CQ CQ »-H PQ CQ mm PQ CQ m CQ inch inch inch inch inch inch inch inch - ϋ 5 &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; s 枨 φ: /--Ν &lt; Comparative example 25 Inventive Example 30 | Inventive Example 31 1 Inventive Example 32 | Inventive Example 33 I Comparative Example 26 Comparative Example 27 Inventive Example 34 Inventive Example 35 Comparative Example 28 ?: ID oo Os s SS rnrii: (Λν) * Rong Umbrella JJKf : ( ο)-蓉伞=^湓埸:ur Rong umbrella AJKHfsifs : (3) ·Rose umbrella^Umbrella field «Cup:(01) 201219599 【21 &lt;】Ji-so inchΖ-Ιί (X7) oo Ο ο 〇o ο ο Ο Ο o 0.31 0.39 0.31 0.25 Ο Ο 〇〇〇〇〇〇(X6) 0.050 0.050 0.050 0.019 0.006 0.088 1 0.125 1 0.050 0.050 ! 0.050 1 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.0 50 0.050 0.050 0.050 (X5) o 0.033 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 (X3) SI S § s SSS s § § (X2) 0.75 0.75 0.75 , 1 0.75 1 0.75 1 0.75 I 0.75 0.75 0.75 0.75 ! 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 · 0.75 0.75 0.75 0.75 (XI) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 inch. — — — yr) inch · — trj — — — — — — ο CO ΓΛ ΓΛ p T}· 〇〇 〇 〇 other wt% mmm CO CO cn mmm CO m cn cn mmm type pro-phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphate phosphate Phospho-pro-phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid comparison example 17 Example 18 Inventive Example 17 Inventive Example 18 Comparative Example 19 Inventive Example 19 Comparative Example 20 Inventive Example 20 Inventive Example 21 Inventive Example 22 Inventive Example 23 Inventive Example 24 Inventive Example 25 Inventive Example 26 Inventive Example 27 Comparative Example 21 Comparative Example 22 Inventive Example 28 Inventive Example 29 Comparative Example 23 Comparative Example 24 Comparative Example 25 Inventive Example 30 d Z fn v〇cn Pi 00 σ\ m Ο 5 5 〇\ 〇«ο (N ^Τ) 201219599 J-asso 寸ο 〇Ο ο Ο 〇 〇〇0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 +/- 0.004 0.40 0.40 0.40 0.40 0.40 0.40 0.40 S § § § § § § 0.75 1 0.75 I 1 0.75 1 1 0.75 1 1 0.75 1 0.75 | 0.75 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 — — — in inch 'mm·mmmm ΓΟ ΓΟ orthophosphoryl prophosphate phosphate phosphatidyl phosphate phosphatidyl phosphate phosphoric acid Invention Example 31 Inventive Example 32 Inventive Example 33 Comparative Example 26 Comparative Example 27 Inventive Example 34 Inventive Example 35 Comparative Example 28 OO «Λϊ ON § S (ΐν) / ϊ) = ζ.χΛυ+ΐ&lt;) / ("ο) H9xIAlu+'PQ+&lt;) / rsd) &quot;ςχΑρα) / (&gt;Η)=inchχ * (ρ α) / (υ) = εχ (υ+m+v) / (υ) =ζχ - (υ+m+v) / (3⁄4) =ιχ {:※) 201219599 [I-(NI sJ-alrlso inch ΓΖΙ &lt; (W) Solid content 〇Ο o ο ο ο Ο ο Ο ο Ο Ο ο ο Ο ο ο Ο ο ο Relatives 1 1 1 II 1 III 1 III 1 I 1 IIII /-~N o V— / Η ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ;Η α b Mo conversion S? 〇VO ο VO d VO ο ν〇ο νο ο ν〇ο ο ν〇ο ν〇ο ν〇ο ν〇Ο ν〇ο ν〇Ο ο ν〇ο VO ο ν〇 Ο ν〇ο 〇ο VO &lt; 5: ε ε S: ε: Ε U: 5: Ξ 5: Ε ίΖ ω Sw/ V conversion inch Ο inch ο inch ο inch ο inch ο inch ο inch ο inch ο寸 inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch Η ω *-Η ω W r&quot;H ω ω W ψ-^ W »—Η m /—NQ s—/ Ti conversion I FH ^Η ^-^ ^-Η »—Η Ο *—Η »-Η Types &lt; QQ Ρ Q ^Η Ρ Q ^-Η Q Ρ »-Η Q · Q 1&gt;-Η QQQ »&quot;Η QQQQQ Ο Ω /—N u S—/ Solid component ss SSSSSSSSSS δ S s § § S Type u FH u υ »-Η τ—Η 1··^ υ U υ r—^ υ υ υ Ο υ υ 2 /— N PQ N^·/ Solid content VO VO ν〇ν〇\〇ο 2 ν〇VO ν〇ν〇ν〇ν〇 beam! View rN &lt; 0Q rH 0Q »&quot;Η CQ ΏCQ CQ ^-Η CQ PQ 0Q fH m 0Q »-Η CQ Η CQ CQ PQ (Ν CQ ΓΟ CQ inch 0Q ι〇CQ PQ &lt;3 'Sw/ solid The amount of ingredients is 1 inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch &lt;&lt;ν〇&lt; 卜 &lt; 00 &lt; ΟΝ &lt; ο &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; κη C v〇&lt;卜 &lt; 00 C &lt; 00 C &lt; Η C &lt; C ψ-^ &lt; Inventive Example 36 Comparative Example 29 Comparative Example 30 Comparative Example 31 1 Comparative Example 32 Comparative Example 33 1 Inventive Example 37 1 Inventive Example 38 Inventive Example 39 Inventive Example 40 Comparative Example 34 Comparative Example 35 Comparative Example 36 Comparative Example 37 Comparative Example 38 Inventive Example 41 Inventive Example 42 Comparative Example 39 Comparative Example 40 Inventive Example 43 z 00 ν〇$ ο CS Ρ jn Ρ 00 σ\ g oo CN 00 m 00 Inch 201219599 J-asso inch ooo 〇o /-NU ___, \ΐϊν 1 1 • 1 1 inch inch inch inch a inch a inch inch inch inch av〇o O ov〇Ο v〇〇v〇o (N PH &lt; N tlH (N PLh (N to ci inch o inch Ο Ο inch 〇Ξ CN ω &lt;N ω CN ω CN ω QQQQHQ § s § § § 〇UUU jm condensate CQ V—✓ f? VO ν 〇 VO v 〇 Q Q Q Q Q Q Q & & & & & & & & & & & & & & & & & & 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 s 00 \〇00 SS 00 oo is .· , .· s , f .· £ - .. s - .. § 201219599 [3-31 &lt;] Jus'so inch (X7) ooo ο 〇〇〇〇〇 〇〇〇〇〇〇〇Ο Ο 〇〇ο oo (X6) 0.050 0.050 0.050 0.050 0.050 0.050 0.050 | 0.050 0.050 0.057 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.048 0.050 0.050 0.050 (X5) 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.008 0.008 (X4) 0.40 0.40 0.40 0.40 0.40 0.40 0.43 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.44 (X3) S § § § § § ν〇in ss (X2) 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 ί | 0.75 | 1_2^1__1 1_0^5_1 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.76 0.75 0.75 0.75 (XI) 0.20 0.20 0.20 0.20 0. 20 0.20 0.20 0.20 0.13 | 0.23 | 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.19 0.20 0.20 0.20 pH value - inch · to — V) ri- inch · — in — inch · inch · W-1 ¥ — ΙΛϊ — yr — in other wt% m cn mmm CO mmmm cn mmm type pro-phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphate phosphate Phospho-pro-phosphoric acid phosphoric acid phosphoric acid Example 36 Comparative Example 29 Comparative Example 30 Comparative Example 31 Comparative Example 32 Comparative Example 33 Inventive Example 37 Inventive Example 38 Inventive Example 39 Inventive Example 40 Comparative Example 34 Comparative Example 35 Comparative Example 36 Comparative Example 37 Comparative Example 38 Inventive Example 41 Inventive Example 42 Comparative Example 39 Comparative Example 40 Inventive Example 43 Comparative Example 41 Inventive Example 44 Inventive Example 45 No. 5〇00 Ό $ 〇CN rn VO 00 On g 00 〇〇CO 00 00 v〇 00 6 inch 201219599 J-asso inch o 〇0.050 0.050 0.008 0.008 0.40 0.40 S § 0.75 0.75 0.20 0.20 — ^T) mm orthophosphate phosphoric acid inventive example 45 invention example 46 S5 00 00 og+πν) / OM) =ζ.χ - ou+em+%0 / (Ια) =9X . (u+m+&lt;) / (—5=ςχ · (pa) / (&gt;3)= Inch x &lt; (ρα) / (u) = εχ &lt;(u+Da+&lt;) / (u) =3⁄4 (u+CQ+&lt;) / (m) =ix {:※) 201219599 40035pif [ Table 13-1] Table 13-1 No. Silver plate drying temperature °c Adhesion amount g/m2 Remark 1 Inventive Example 1 GF1 100 1.0 2 Inventive Example 2 GF1 100 1.0 3 Inventive Example 3 GF1 100 1.0 4 Comparative Example 1 GF1 100 1.0 5 Inventive Example 4 GF1 100 1.0 6 Inventive Example 5 GF1 100 1.0 7 Comparative Example 2 GF1 100 1.0 8 Comparative Example 3 GF1 100 1.0 9 Comparative Example 4 GF1 100 1.0 10 Comparative Example 5 GF1 100 1.0 11 Comparative Example 6 GF1 100 1.0 12 Comparative Example 7 GF1 100 1.0 Reference Japanese Patent No. 3883831 No. 13 Comparative Example 8 GF1 100 1.0 14 Comparative Example 9 GF1 100 1.0 Reference Patent Publication No. 2006-152436 No. 15 Inventive Example 6 GF1 100 1.0 16 Inventive Example 7 GF1 100 1.0 17 Inventive Example 8 GF1 100 1.0 18 Inventive Example 9 GF1 100 1.0 19 Comparative Example 10 GF1 100 1.0 20 Inventive Example 10 GF1 100 1.0 21 Inventive Example 11 GF1 100 1.0 22 Comparative Example 11 GF1 100 1.0 23 Comparative Example 12 GF1 100 1.0 24 invention 12 GF1 100 1.0 25 Inventive Example 13 GF1 100 1.0 26 Comparative Example 13 GF1 100 1.0 27 Comparative Example 14 GF1 100 1.0 28 Inventive Example 14 GF1 100 1.0 29 Inventive Example 15 GF1 100 1.0 30 Comparative Example 15 GF1 100 1.0 31 Inventive Example 16 GF1 100 1.0 32 Comparative Example 16 GF1 100 1.0 33 Comparative Example 17 GF1 100 1.0 34 Comparative Example 18 GF1 100 1.0 35 Inventive Example 17 GF1 100 1.0 36 Inventive Example 18 GF1 100 1.0 37 Comparative Example 19 GF1 100 1.0 38 Inventive Example 19 GF1 100 1.0 39 Comparative Example 20 GF1 100 1.0 40 Inventive Example 20 GF1 100 1.0 51 201219599 41 Inventive Example 21 GF1 100 1.0 42 Inventive Example 22 GF1 100 1.0 43 Inventive Example 23 GF1 100 1.0 44 Inventive Example 24 GF1 100 1.0 45 Inventive Example 25 GF1 100 1.0 46 Inventive Example 26 GF1 100 1.0 47 Inventive Example 27 GF1 100 1.0 52 201219599 [Table 13-2] Table 13-2 No. Plated steel sheet drying temperature °c Adhesion amount g/m2 Remark 48 Comparative Example 21 GF1 100 1.0 49 Comparative Example 22 GF1 100 1.0 50 Inventive Example 28 GF1 100 1.0 51 Inventive Example 29 GF1 100 1.0 52 Comparative Example 23 GF1 100 L0 53 Comparative Example 24 GF1 - - Surface treatment liquid gelled, so the test was aborted 54 Comparative Example 25 GF1 100 0.1 55 Inventive Example 30 GF1 100 0.3 56 Inventive Example 31 GF1 100 0.5 57 Inventive Example 32 GF1 100 1.3 58 Inventive Example 33 GF1 100 1.5 59 Comparative Example 26 GF1 100 2.0 60 Comparative Example 27 GF1 40 1.0 61 Invention Example 34 GF1 60 1.0 62 Inventive Example 35 GF1 140 1.0 63 Comparative Example 28 GF1 220 1.0 64 Inventive Example 36 GF1 100 1.0 65 Comparative Example 29 GF1 - - An undissolved substance was generated, so the test was terminated 66 Comparative Example 30 GF1 - - Generation In the case of undissolved matter, the test was discontinued. 67 Comparative Example 31 GF1 - - produced undissolved matter, so the test was discontinued 68 Comparative Example 32 GF1 100 1.0 69 Comparative Example 33 GF1 100 1.0 70 Inventive Example 37 GF1 100 1.0 71 Inventive Example 38 GF1 100 1.0 72 Inventive Example 39 GF1 100 1.0 73 Inventive Example 40 GF1 100 1.0 74 Comparative Example 34 GF1 - - produced undissolved matter, so the test was terminated. 75 Comparative Example 35 GF1 - - produced undissolved matter, so the test 76 was discontinued. Example 36 GF1 - - produced undissolved matter, so the test was discontinued 77 Comparative Example 37 GF1 100 1.0 78 Comparative Example 38 GF1 100 1.0 79 Inventive Example 41 GF1 100 1.0 80 Inventive Example 42 GF1 100 1.0 81 Comparison 39 GF1 - - Amine ester resin agglomerated, so the test was terminated 82 Comparative Example 40 GF1 - - Amine ester resin coagulation, so the test was terminated 83 Inventive Example 43 GF1 100 1.0 84 Comparative Example 41 GF1 100 1.0 85 Inventive Example 44 GF2 100 1.0 86 Invention Example 45 GF3 100 1.0 87 Inventive Example 45 GF4 100 1.0 88 Inventive Example 46 GF5 100 1.0 53 201219599 [1-inch 1 inch] J-asso inch 'inch one ^ ±1 ✓^N ψ _ Sw/ &lt; XXX &lt; ] &lt;] 0 &lt;&lt; 0 XX 0 &lt;&lt;!&lt;1 0 &lt;] &lt; XX si /—\ Ο **^ V«_X ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ / ^ N 00 ◎ ◎ ◎ ◎ 〇 1 〇 X + ◎ ◎ ◎ ◎ ◎ X ◎ ◎ ◎ ◎ X ◎ ◎ ◎ / · - S 卜 S - ✓ You ii) m BS; meal ◎ ◎ ◎ ◎ i 1 〇 X ◎ ◎ X 〇 + 〇 1 0 ◎ ◎ ◎ ◎ &lt;] ◎ ◎ ◎ 1 \ \ w Q ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 戚 1 1 1 &lt; 6] r—N s—/ ◎ 〇〇X ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ m Bui; Β Β * · · · · · · · ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ΓΛ w Vw / 游 iim ns; meal ◎ ◎ ◎ ◎ ◎ 1 〇 &lt;1 X 〇 XX ο 〇 &lt; ◎ ◎ ◎ ◎ 〇i ◎ 〇 / -&quot;N CN Electric § Γ ◎ % 1 〇X ◎ ◎ ◎ XXX XXX ◎ ◎ ◎ 〇 X X X X s —— ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Φ CN cn Jj inch Φ WJ Φ (Ν jJ ΓΟ aJ inch magnetic Jj νο - Ο 卜 Jj oo o Jj VO 00 〇 \ W 佥〇-ϋ ο 1·^ 佥 Jj 6 2 &lt; Ν inch VC 〇 〇Os 〇&lt;N inch OO 〇 inch 1° 201219599 --£00 inch&lt;3 &lt;] &lt;1 &lt;] &lt;] &lt;1 &lt;] &lt;] &lt;1 &lt;3 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ο &lt;] X 1 〇 ◎ ◎ X 1 〇 1 〇 X ◎ ◎ &lt;1 1 0 1 Ο XX 1 〇1 〇1 〇 ◎ ◎ &lt; 〇 ◎ ◎ X 〇 + 〇 ◎ ◎ ◎ (Ν aJ leather food r〇Φ m Jj inch ¥ in jg&lt; J〇佥VO _1J CN ;q 〇〇CN ON cs co CN m - 201219599 Buck 31 &lt; 】J'alnso inch 'inch1&lt; lubricity (11) &lt;] &lt;] &lt;1 &lt;] &lt;&lt; 0 &lt; ◎ ◎ &lt;] 〇 &lt;] &lt;] &lt;3 &lt;&lt;] Chemical agent gelation, so the test is to sweat (10) ◎ ◎ ◎ 〇 ◎ ◎ ◎ 1 〇 1 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 1 ο Liquid stability (9) Appearance ◎ X ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎涂 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 NI ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ black resistance / * - N inch X ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 对 触 / * * * ◎ ◎ ◎ ◎ 1 〇 X ◎ 0 1 〇 ◎ ◎ ◎ ◎ ◎ 1 〇 1 〇 t ◎ &lt; X /-N (N s - / bending portion ◎ 〇 ◎ ◎ ◎ t 〇 X ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X &lt; 1 〇 + ◎ &lt; X /-NV - ✓ 1 plane 1 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 1 〇〇〇 + ◎ &lt;] X Comparative Example 17 Comparative Example 18 1 Inventive Example 17 I Inventive Example 18 ON aJ Inventive Example 19 Comparative Example 20 Inventive Example 20 Inventive Example 22 Inventive Example 24 Inventive Example 24 Inventive Example 25 Inventive Example 26 1 Inventive Example 27 I Comparative Example 21 Comparative Example 22 Inventive Example 28 | Inventive Example 29 I Comparative Example 23 Comparative Example 24 Comparative Example 25 6 m to yr Cn VO m P; 00 mo inch 3 3 5 !7&gt; CN in

9S 201219599 JUS£oo inch

&lt;3 &lt;3 &lt;3 &lt;&lt;&gt;&lt;&lt;&gt;&lt;&gt; & ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ t 〇 &lt;&lt; 〇 ◎ ◎ ◎ ◎ ◎ XX XX & & & & 〇 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ I Ο 1 0 ◎ ◎ ◎ X % ◎ ◎ I Ο 1 0 ◎ ◎ 〇〇i ◎ 0 0 + 0 ◎ ◎ ◎ 〇i ◎ ◎ (S m Φ mm 苳£ Jj 佥&lt;Γ) m 00 (N 苳jj ^Ti V〇00 〇\ SS 201219599 Ε-inch I&lt;] Jidgso inch jo P Μ π; 〇〇- &lt;] &lt;] &lt;] &lt; ο 0 0 &lt;&lt;]&lt;1&lt;]&lt;3&lt;1 ◎ Two VJ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Liquid stability / - Ν 〇 \ Appearance ◎ ◎ X ◎ ◎ ◎ ◎ ◎ X ◎ ◎ ◎ ◎ ◎ ϊ oo oo ◎ L undissolved Therefore, in the suspension test, undissolved matter was generated in the production stage of the treatment liquid, so that the test was stopped and the undissolved matter was stopped, so the test was stopped. ◎ ◎ ◎ ◎ ◎ Undissolved matter, Μ Θ Θ Θ 珑 ? ? ? ? ? ? ? ? ? ? ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ /*~N ν〇S—/ Not degreased ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ In the production stage of the treatment liquid, the amine ester resin is condensed in the production stage of the treatment liquid to condense the amine ester resin ◎ 〇 ◎ Discoloration»T&gt; V-✓ ◎ -5- Then Z * ◎ ◎ ◎ ◎ ◎ ◎ ΤΤ 1 ΰ - T71 - B- ◎ ◎ ◎ ◎ ◎ ◎ ◎ «&lt; Μ /-N inch Sw / ◎ s PM.IW phase '1 W? 〇〇 ◎ 〇 ◎ ◎ taj S? Shouting Zhao Q^l Lock shouting ◎ ◎ ◎ 〇 ◎ For money / ^S ΓΛ After skimming ◎ X 〇 ◎ ◎ 〇 ◎ X 〇 ◎ 〇 ◎ X ◎ /*-\ (N s - / Bending portion ◎ X &lt;] ◎ 〇 ◎ ◎ X &lt; 1 ◎ ◎ ◎ &lt;] ◎ /-N 1 plane portion ◎ &lt;3 ◎ ◎ ◎ ◎ ◎ &lt; ◎ ◎ ◎ ◎ ◎ 1 Inventive Example 36 1 Comparative Example 29 Comparative Example 30 Comparative Example 31 "Comparative Example 32 | Comparative Example 33 Inventive Example 37 Inventive Example 38 EXAMPLE 39 Inventive Example 40 Comparative Example 34 Comparative Example 35 Comparative Example 36 | Comparative Example 37 I Comparative Example 38 Inventive Example 41 Inventive Example 42 Comparative Example 39 Comparative Example 40 Inventive Example 43 | Comparative Example 41 | Inventive Example 44 No. s ίο 〇〇 VO ν〇〇&lt;Ν ΓΠ Γ^· 00 S 〇〇 (N 00 m 00 S yr\ 00 201219599 J-asso 寸 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 $ v〇00 00 00 201219599 4UU35pif As shown in Table 14, 'Test steel sheets produced using the surface treatment liquid of the present invention have excellent corrosion resistance (planar portion) , processing part, after degreasing), blackening resistance, heat discoloration resistance, applicability (after degreasing and degreasing), solvent resistance, liquid stability and sweat resistance. On the other hand, in Comparative Example 1 (Ν〇.4) outside the scope of the present invention, since the content of the cationic amine ester resin emulsion (B) is less than the range of the present invention, corrosion resistance and heat resistance of the bent portion are not obtained at all. Lubricity is also poor. In Comparative Example 2 (No. 7), since the content of the cationic amine ester resin emulsion (B) exceeded the range of the present invention, the quality after alkali degreasing was poor, and the solvent resistance was not satisfactory. In Comparative Example 3 (Νο·8) and Comparative Example 4 (No. 9), since the organic titanium chelate compound (D) according to the present invention was not formulated, the quality of the bending work portion could not be obtained. In Comparative Example 5 (No. 10), Comparative Example 7 (No. 12), and Comparative Example 8 (No. 13) in which the tetravalent vanadium compound (E) was not blended, the corrosion resistance of the bent portion was not obtained, and the lubricity was also difference. In Comparative Example 6 (N〇 u), since a pentavalent hunger compound was used, the f-curved portion or the degreasing property was not obtained, and the coating property after alkali degreasing was lowered. Comparative Example 9 Μ) Although the tetravalent compound (8) was used, the content of the cationic amine vinegar resin emulsion (8) was outside the range of the present invention, so that the material curing portion or the agent property could not be obtained. Further, the comparative example 7 was tested with reference to the plated steel plate of the third (3) /-, and the comparative example 9 was tested with reference to the galvanized steel sheet disclosed in Japanese Patent Publication No. 2006-152436. 'Opening Comparative Example 10 (No. 19) Since the amount of the Shi Xi Hyun coupling agent (c) is not in the range of the present invention, (4) the solvent property is poor, and the other is a comparative example 201219599 4 (JU3^pif η (Νο·22) due to The amount of the solid content is outside the range of the present invention, so that the rigidity of the substantially curved portion cannot be obtained. Comparative Example 12 (No. 23) is a decane coupling agent (c) of titanium with respect to the organic titanium chelate compound (D). Since the solid content is outside the range of the present invention, the corrosion resistance or the coating property after alkali degreasing is inferior, and in Comparative Example 13 (No. 26), since the solid content is less than the range of the present invention, the corrosion resistance of the bent portion cannot be obtained. The storage stability of the surface ^ is poor. = Comparative Example 14 (Νο·27) The hunger of the tetravalent hunger compound (8) relative to the organic titanium chelate compound (D) = titanium = does not satisfy the requirements of the present invention. On the other hand, the amount of (10) ίί in Comparative Example 15 (N〇.30) is beyond the range of the hair _ range, so the resistance-recording compound (denier 1^) after degreasing, comparative example η (Ν〇 .33) due to poor acidification. Others satisfy the scope of the present invention, and are all resistant to blackening. 34·34) Since the above-mentioned solid content excess (^ΓΖ, 37) is a characteristic of the present invention in the range of ^ 5 20 5 0 ^, the resistance is poor. Since the above 111 body component amount exceeds the present invention 22 (ί:= Comparative Example 21 (N..48) of the pH value, and the durability of the comparative example. PH letter ^Example 23 (N〇.52) could not obtain the gelation of the bent portion, so that there was no ^24 (Να53), in the case of the surface treatment liquid 201219599 and the case 25 (Νο·54), the amount of adhesion of the film did not satisfy the scope of the present invention, and sufficient richness could not be obtained. In addition, the comparative example % (Νο. 59) Since the adhesion amount of the film is outside the range of the present invention, the coating property is lowered. ^Example 27 (Νο. 60) The drying temperature does not satisfy the specifications of the present invention, and the method obtains the yield and coating property after degreasing. , Comparative Example, 63) Since the drying temperature is outside the range of the present invention, the corrosion resistance or coating property of the bending force is lowered. The force is in the resin compound (Α), Comparative Example 29 (ν. (6), comparable to 0石山34 (Νο.74) and Comparative Example 35(10) are in the range beyond the scope of the present invention. 'Comparative example' Comparative Example 36 (Ν .76) the number of substitutions of the fluorenyl group, the production stage of the surface treatment liquid ft, the comparative example 32 (Νο. 69), and the comparative example 37 (the average value of the glutinous solution = is outside the scope of the present invention, Therefore, the basis and the resistance after degreasing. Comparative Example 33 (Ν / 曲加工 (Νο.78) due to the average polymerization of sulfhydryl groups compared to Example 38 bending part of the coffee and storage stability ^ degree beyond the scope of the present invention In the case of Comparative Example 39 (Ν〇·81), an amine ester resin emulsion example 4 was used. (10) 2) The medium amine_emulsion is another resin in the preparation stage of the surface treatment liquid, so (Νο. 84) is the corrosion resistance of the Wei coupling agent after the alkali degreasing of the invention of the invention. [Industrial Applicability] 62 201219599 4UU35pif According to the present invention, it is possible to provide a corrosion resistance (especially after a bent portion and an alkali degreasing) without using a chromate treatment, and heat resistance and coating A surface-treated plated steel sheet excellent in properties, solvent resistance, and sweat resistance. [Simple description of the diagram] None. [Main component symbol description] 益〇 63

Claims (1)

201219599 External uo^pif VII. Patent application range: 1. A surface treatment liquid for a plated steel sheet, which is characterized in that it satisfies the following conditions (1) to (6) and contains the following components, and the pH value 4 to 5: a resin compound (A) having a bisphenol skeleton represented by the following general formula (I); having at least one cationic functional group selected from the group consisting of a primary amino group to a tertiary amine group and a quaternary ammonium salt group Base cationic amine ester resin emulsion (B); one or more decane coupling agents having at least one reactive functional group selected from the group consisting of an active hydrogen-containing amine group, an epoxy group, a fluorenyl group, and a methacryloxy group C); organotitanium chelate compound (D); tetravalent vanadium compound (E); molybdic acid compound (F); fluorine compound (G); and water (H); (1) relative to the above resin compound ( A), the cationic amine ester resin emulsion (B) and the above-mentioned decane coupling agent (C), the total solid content of the compound {(As) + (Bs) + (Cs)}, the cationic amine ester emulsion (B) The solid content (Bs) is 0.10 to 0.30 in terms of a weight ratio [(Bs) / {(As) + (Bs) + (Cs)}]; (2) relative to the upper The total solid content of the resin compound (A), the above cationic amine ester resin emulsion (B), and the above decane coupling agent (C) is 64 201219599 40035pif amount KAS) + (Bs) + (cs)}, the above decane coupling agent (c) The solid content (Cs) is 0.60 to 0.85 in terms of a weight ratio [(cs) / {( As) + (Bs) + (cs)}]; (3) relative to the above-mentioned organic titanium chelate compound (d) The amount of titanium (DTi), the solid content (Cs) of the above decane coupling agent (C) is 50 to 70 by weight ratio {(Cs) / (DTi)}; (4) Chelating with respect to the above organic titanium The amount of titanium (DTi) of the compound (d), the amount of hunger (Ev) of the above-mentioned tetravalent compound (E) is in the order of weight: 0.30 to 0.50 in terms of {(Ev) / (Dti)}; The above-mentioned molybdic acid is the total solid content {(As) + (Bs) + (Cs)} with respect to the resin compound (A), the cationic amine ester resin emulsion (B), and the decane coupling agent (c) described above. The amount of molybdenum (FM) of the compound (F) is 0.003 to 0.03 in terms of a weight ratio [(FmJ/Raj + (Bs) + (Cs))]; (6) Relative to the above-mentioned resin compound (a), the above cation Amine ester resin emulsion (B) and the above-mentioned decane couple The total solid content of the agent (c) {(As) + (Bs) + (Cj}, the fluorine equivalent amount (Gf) of the above fluorine compound (g) is in a weight ratio [(GF) / {(As) + (Bs ) + (Cs)}] is counted as 0.01~0.1; [Chemical] 65 • · · (1) 201219599 4UU3^pif OH In OH ^ (), the key, 纟. The thiol group represented by the formula (8) or the formula (III) in which the benzene ring 1 and the oxime 2 are respectively independent of each other, and the average number of substitutions per benzene fluorenyl group is G.2 to 1 0. ; η table is an integer of 2 50; '[2] - ch2~n [Chemical 3] In the formula (III), Ri, R2, &amp;, heart and &amp; are independent of each other. 7) hydrogen, carbon having a carbon number of 1 to 10 or a transalkyl group having a carbon number of 1 to 〇, A · indicates a helium ion or an acid ion. The surface treatment liquid for galvanized steel sheets according to the first aspect of the invention, wherein the surface treatment liquid further contains wax (W), relative to the resin compound (A) and the cationic amine ester tree. The solid content of the lunar emulsion (B) (the total solid content ({Aj + 丨, the above ant ^)) is in the weight ratio [(\\^)/{(\) + (33)} ], in the range of 0.2 to 0.4. ^ A method for producing a galvanized steel sheet, characterized in that the amount of the surface treatment liquid as described in the application range ί 1 or 2 is reduced to 2 g/m 2 to 18 g per side. The range of /m2 was applied to the surface of the steel plate, and then the plate temperature was 5 。. 〇~18〇. 〇 4. A galvanized indium bismuth, in the 矣 矣.. g/m2 ~ The surface treatment film is to be as described in the scope of the patent application or the first to the first, and to reach a plate temperature of 50. The surface treatment liquid of 〇~ was applied to the surface of the steel sheet and dried at 180 ° C to obtain. 67 201219599t IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: No 0 201219599 4UUJ5pifl is the Chinese manual of No. 100134328. There is no slash correction. This amendment date: January 12, 2012 invention patent specification (the format of this manual, Order and bold characters, please do not change any more. ※Please do not fill in the ※ part. ※Application number:丨※Application date: Category: I. Name of the invention: (Chinese/English) Surface treatment liquid for galvanized steel sheet and plating Zinc steel plate and its manufacturing method SURFACE TREATMENT LIQUID FOR ZINC OR 0 ZINC ALLOY PLATED STEEL SHEET, ZINC OR ZINC ALLOY PLATED STEEL SHEET, AND METHOD OF PRODUCING THE STEEL SHEET II. Abstract of the Invention: According to the present invention, by each A specific resin compound having a bisphenol skeleton, a cationic amine ester resin emulsion, a decane coupling agent, an organic chelating compound, a tetravalent cerium compound, a ceric acid compound, a fluorine compound, and water are formulated in proportion, and the pH is set to 4~5, can obtain the bending of the steel plate formed on the surface of the metal tantalum material Choi portion of the money, solvent resistance after alkaline degreasing coatability, film excellent in sweat resistance of chromium-free surface treatment liquid. Abstract: In particular, a specific resin, a bisphenol frame, a cationic urethane resin emulsion, a silane coupling agent, an organic titanic chelate compound, a tetravalent vanadium compound, a 1 201219599 4UU35pill is 100134328 No. Chinese manual, no slash correction, date of revision: January 12, 2012, invention description: [Technical field of invention] The present invention relates to a most suitable use for automobiles, home appliances, building materials, and particularly during manufacturing and manufacturing. An environmentally-friendly galvanized steel sheet containing no chromium or the like and a method for producing the same. The present invention relates in particular to a surface treatment liquid useful for improving the sweat resistance and the like of a galvanized steel sheet. [Prior Art] For the purpose of improving the corrosion resistance (white rust resistance, red embossability) for the surface of galvanized steel sheets for steel sheets for steel products, steel sheets for building materials, and steel sheets for automobiles, A chromate-treated steel sheet is treated with a treatment liquid containing chromic acid, dichromic acid or a salt thereof as a main component. This chromate treatment is an economical treatment method which is excellent in economics and can be carried out relatively easily. The chromate treatment uses hexavalent chromium as a pollution-restricting substance, but the hexavalent chromium is treated by the blue (four) system (dGsed coffee), and is completely reduced and recycled by A without being released into nature. By the action of the film, the dissolution of chromium from the chromate film can also be almost Si. T will pollute the environment or the human body due to hexavalent chromium. However, the use of the movement ^a ^ ball is a problem, want to autonomously reduce the hexavalent chromium itself. 4 (sh^sO due to the above situation] in order to prevent the production of white ore from the zinc steel plate, a large number of 201219599 41 several mplfl correction Date: January 12, 2012 is the 10th m328 Chinese manual. There is no scribe correction. This paper proposes a treatment technology that does not use chromate treatment, so-called chromium-free technology, such as the use of inorganic compounds, organic compounds, organic polymers. Materials or compositions in which these materials are combined to form a surface-treated film on a galvanized steel sheet. However, various useful techniques have been proposed so far, but with the introduction of these chromium-free technologies, 'new confirmation has been made so far. The problem to be solved that has not yet been recognized. The first problem is the improvement of the corrosion resistance of the processed portion of the surface-treated plated steel sheet. The surface-treated galvanized steel sheet is processed (cut, bent, and welded). However, when the wire product is subjected to bending processing, the surface is plated and stretched on the front side of the bent portion. That is, the surface treatment is performed along with the above-mentioned 'cutting process. When the crucible is also stretched, the surface treatment film is damaged and the galvanized surface is exposed, and the deterioration of the resistance of the exposed portion is a problem. Especially in the case of the curvature processing, it is not a local damage like extrusion, but continuous. The film and the plating are damaged, so it is often difficult to obtain the corrosion resistance of the processed portion. The second problem is to ensure the solvent resistance of the surface treated film. In the above θ Μ :, the solvent may be used to adhere the oil on the surface of the film. Knocking off or erasing with a marker written in a mark of ink (magic), at this time, the phenomenon that the surface treatment film peels off or whitish and discolors (whitening) due to the solvent is frequently observed. In the case of the surface treatment skin __, When the surface treatment film is whitened, the appearance of the surface is reduced. The second problem is to ensure the coating property of the surface treatment film. The surface treated galvanized steel sheet processed as described above sometimes For the time being, use the alkali cleaning agent, etc. 5 201219599 40035pifl is the Chinese manual of No. 100134328. There is no slash correction. This revision date: 2〇12年12月12臼(test degreasing), so that the surface is clean and sometimes the demand is _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Denaturation. When the environment is high in humidity or high temperature, it is easy to produce a hard-to-expose phenomenon of blackening. Black. It is especially noticeable when it has an I: layer containing two &amp; ''black', so it is galvanized. Steel plate work: Prime: Mine is excellent for blackening resistance. The fifth problem is to ensure the sweat resistance of the surface treated film. :: When the touched part changes to black with time:: i The human sweat adheres to the steel plate and the surface of the steel plate becomes:, color, phenomenon. Therefore, the surface treated film of the zinc-zinc steel sheet is also adhered to black, that is, it is excellent in sweat resistance. As described above, it is desirable to carry out a zinc-zinc steel sheet having various surface treatments excellent in characteristics. Here, 'the technique of the prior and chromium-free (four) is as follows: that is, Patent Document 1 discloses that an aqueous solution containing a water-dispersible ceria, an alkyd resin, and a trialkoxy decane compound is applied to A method of forming a film by drying a metal surface. In addition, in Patent Document 2 and Patent Document 3, a surface treatment method for imparting corrosion resistance to a metal material using a water-soluble resin containing a hydroxypyrone compound derivative, and an aqueous solution using a hydroxystyrene compound are disclosed. Or a water-dispersible polymer to impart corrosion resistance to a metal material. 201219599 40035pifl is the Chinese manual of No. 100134328. There is no slash correction. This revision date: January 12, 2012, and then, 'Patent Document 4 discloses that a water-based resin, colloidal cerium oxide, and ammonium glutamine are used in a specific ratio. The technology of surface treatment agents. However, none of these techniques has developed a film that imparts a survivability resistance to a chromate film. In addition, Patent Document 5 discloses a technique of surface-treating a film containing an organic resin and a sulfur-containing carbonyl compound, but the corrosion resistance after alkali degreasing is not sufficient. Patent Document 6 discloses a technique for treating a surface of a metal plate by using a treatment liquid containing an organic resin, a decane coupling agent, and a solid lubricant in an aqueous solution of a broken acid, but since the inorganic component is likely to form a hard polymer, the bending is performed. The corrosion resistance of the processed portion such as the folding process is insufficient. Further, since the metal is included, the secondary adhesion of the coating is poor. Patent Document 7 discloses a technique of forming a resin film by using a resin aqueous solution containing a carboxyl group-containing polyurethane resin, an ethylene-unsaturated carboxylic acid copolymer aqueous dispersion 'cerium oxide particle, and a decane coupling agent in a specific ratio, but _ Solvent or processing department is not adequately resistant to surnames. Patent Document 8 discloses a steel sheet having a film containing an amine ester resin, a lubricant, an inorganic colloidal compound, and a decane coupling agent in a specific ratio, but the steel plate is designed on the premise of electroplating, although plating The coating property is excellent, but the processing part is not sufficient for the surname. Patent Document 9 discloses a surface treatment liquid obtained by mixing a decane coupling agent with an amine ester resin and adjusting the pH to 2.5 to 4.5. However, the alkali degreasing has poor corrosion resistance and insufficient solvent resistance. Patent Document 10 discloses a method for using a specific ratio of water-containing 7 201219599 ^UUJDpiIl Modified period: January 12, 2012 is No. 100134328 No-line correction of the dispersion resin, cerium oxide particles and organic titanate The treatment liquid is used to form a film, but the corrosion resistance of the processed portion is insufficient. Patent Document 11 and Patent Document 12 each disclose the use of a specific aqueous epoxy resin dispersion, an amine ester resin dispersion, a decane coupling agent, a phosphoric acid and/or a phosphoric acid compound, and one to five in one molecule. There is a technique for forming a film by a treatment liquid of a fluorine compound, but there is room for improvement in profitability or coating property after degreasing due to the fact that the testability is more or less insufficient. In addition, there is room for improvement in the resistance of the processed portion or the solvent resistance. Patent Document 13 discloses a technique for forming a film using a treatment liquid containing a specific resin compound, a vanadium compound, and a metal compound containing a specific metal. However, since the alkali resistance is insufficient, the corrosion resistance after alkali degreasing cannot be obtained. In addition, problems such as yellowing during heating are unresolved. Patent Document 14 discloses a method of forming a film by using a treatment agent containing a specific resin compound, a cationic amine vinegar resin having a cationic functional group, a ceramide coupling agent having a reactive functional group, a Ti compound, and an acid compound in a specific ratio. Technology. According to this technique, a film having excellent corrosion resistance or excellent fingerprinting property can be obtained. However, the corrosion resistance after alkali degreasing, the durability of the processed portion, and the solvent resistance have not been studied, and there is room for improvement in suppression of these properties. . Patent Document 15 discloses a technique relating to a surface treatment agent containing at least one aqueous resin selected from cationic and nonionic amine ester resins, a specific resin compound, a metal compound containing a specific metal, and water. Regarding the alkali resistance, the resistance to the surname and the solvent resistance of the processed portion, no research has been conducted 'these characteristics cannot be sufficiently obtained. 201219599 40035pifl Revision date: January 12, 2012 is the 10013434 Chinese specification. There is no slash correction. The rs Γ Γ 有 有 1 1 使用 使用 使用 使用 阳离子 阳离子 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The technique of surface treatment agent, titanium, and the study of the inclusion of a special metal, which are not sufficient: 'solvent resistance or coating property is not made in the prior art. Patent Document Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Patent Document 6 Patent Document 7 Patent Document 8 Patent Document 9 Patent Document 10 Patent Document 11 Patent Document 12 Patent Document 13 Patent Document 14 Patent Document 15 〇〇 Patent Document 16 [Summary of the Invention] Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Publication No. 2000-248369, Japanese Patent Application Laid-Open No. Hei No. Hei 11-58599, Japanese Patent Laid-Open No. Hei. Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. 2003-155. 2001-181860, Japanese Patent No. 3883831, Japanese Patent No. 4074044, Japanese Patent Laid-Open No. 2006-152436, No. 9201219599, 40035pifl, No. 8 Chinese, said duck no line correction, this revision period: The U.S. U.S. issue provides a film which is excellent in corrosion resistance on the surface of a metal material, and also has corrosion resistance in a bent portion, corrosion resistance after alkali degreasing, solvent resistance, and applicability after alkali degreasing. A chromium-free surface treatment liquid for galvanized steel sheets excellent in blackening resistance and excellent in sweat resistance, and a galvanized steel sheet using the surface treatment liquid and a method for producing the same. In order to advantageously solve the above various problems, the inventors and others have conducted intensive studies. Human results have been discovered by using a specific resinized mouth, a specific cationic amine ester resin emulsion, a decane coupling agent having a specific functional group, a specific organic Ti chelate compound, and a tetravalent value in a specific ratio. The surface treatment liquid of the compound or the carboxylic acid compound and the fluorine compound treats the surface of the galvanized=reverse surface, which can form a film excellent in resistance to recording, and is resistant to FT coating, black denaturation, and (5) excellent sweat film. In addition, the present invention is based on such a finding, and the main structure of the present invention is as follows: i. A surface treatment liquid for a plated steel plate, characterized by: (1) The following components are contained in the range of the conditions of (6), and the resin having a bisphenol skeleton represented by the formula (1) at pH (A) 7 is selected from the group consisting of an amine group to a tertiary amine group and a cationic amine vinegar resin emulsion (Β) of a cis-functional group in a quaternary ammonium group; an oxyamino group, an epoxy group, a group and a methyl propylene group, more than one reactive functional group Decane couple 10 201219599 4U035p Ifl revised period: January 12, 2012 is No. 100134328 Chinese specification without underscoping correction agent (C); organic titanium chelate compound (D); tetravalent ruthenium compound (E); molybdic acid compound (F ); rat compound (G); and water (H); ❹ ❹ (4) day ί1) (d) total solid content of the upper simple lipid compound (4), the upper ionic amine = lunar emulsion (8) and the above-mentioned Wei coupling agent (6) ,··,:曰,+(Cs)} 'Cational amine vinegar resin emulsion (8), solid = component amount (8) by weight ratio [(Bs) / shape) + material ^ 2) (d) in the above-mentioned compound (A) The total content of the solid components of the above cationic amine = hydrazine emulsion (B) and the above-mentioned oxalate coupling agent (c) (6) solid formation of the wei coupling agent (C) = (CS) by weight ratio [(Cs) / { (As) + (Bs) + is calculated as 0.60 to 0.85; ; J y ) is a chain-converted amount of the above-mentioned organic cerium chelating compound (D) as compared with the solid content of the upper/T-coal coupling agent (C) (Cs) The weight ratio of KCS) / (DTi)} is 5 〇 to 7 〇; )) relative to the above-mentioned organic titanium chelating compound (D) 钦 conversion amount Ή: the above-mentioned tetravalent ruthenium compound (8)丨(6)/叫丨料丨~G5G; ^ 6 The purpose of the above-mentioned resin compound (A), the above-mentioned cationic amine oxime (8) and the above-mentioned dip coupling agent (c) solid content total 11 201219599 4U 〇 35pitl is the 10013434 Chinese manual without line Amendment of this revision date: {(As) + (Bs) + (Cs)} for the 12th day of January 12, 12, the indium conversion amount of the above-mentioned | acid compound (F) (FM. ) is 0.003 to 0.03 in terms of a weight ratio [(Fmj/{(As) + (Bs) + (Cs))]); (6) relative to the above resin compound (a), the above cationic amine ester resin emulsion (B) And the total solid content of the above-mentioned decane coupling agent (c) {(As) + (Bs) + (cs)}, the fluorine conversion amount (gf) of the above fluorine compound (〇) is by weight [[gf) / {( As) + (Bs) + (Cs) ' is counted as 0.01 to 0.1; SJ [Chemical 1] OH Υι HgC-C-CH3 - CHr (I ) OH In the formula (I), 1 and 丫 2 bonded to the benzene ring are each a single atom or a compound represented by the formula (H) or the formula (III), which is a z-group of a benzene ring. The average of the substitution numbers is 〇2~1〇; 'Integers per 50; Double not 2~ [Chemical 2] 12 201219599 4UUJ3pifl = No change to the Chinese manual for the 100134134328 revision period: 2〇12 years! December 12th CH2-N ^2 I ) [Chemical 3] /3⁄4 + / —ch2~n—r4 a~ . ·· (III) o , In the formula (n\ and (III), Rl, r2, R3, 仏 and r5 are independent of each other. a non-hydrogen atom f, an alkyl group having a carbon number of 丨~(7) or a hydroxyalkyl group having a carbon number of i to 10, and A_ represents a hydroxide ion or an acid ion. 2. Surface treatment for a plated steel sheet according to the above 1 a liquid, wherein the surface treatment liquid further contains a wax (W), and the solid content (Ws) of the wax (W) is a total amount of (4) relative to the resin compound 〇 (A) and the cationic (8) component (8). The weight ratio of As) + (Bs)} is [(Ws) /{(As) + (bs)}], in the range of 〇·2~0.4. 3·——Manufacturing method of galvanized steel sheet' In the surface treatment liquid according to the above 1 or 2, the amount of adhesion after drying is applied to the surface of the galvanized steel sheet in the range of 2 g/m 2 to 1.8 g/m 2 per one surface, and then The plate temperature is 503⁄4 to 180 ° C for drying. 屯 A zinc-plated steel plate has a surface-treated film with a surface adhesion amount of g/m 2 to 1.8 g/m 2 on the surface. The plated steel plate is characterized by: 13 201219599 40035pifl for the 100th No. 134328 Chinese Remuneration No-Line Correction Revision Date··2012年月月12曰 The surface treatment film is applied to the surface of the steel sheet as described in the above 1 or 2 to reach a plate temperature of 50 °C to 180X: obtained by drying. [Effect of the Invention] According to the present invention, it is possible to form corrosion resistance and solvent resistance of a bent portion having a corrosion resistance which is not inferior to that of a chromate film and which is introduced in a manufacturing process. A coating film having excellent coatability, blackening resistance, and sweat resistance after alkali degreasing can obtain a chromium-free slag-free zinc steel sheet which is more practical than the prior art. [Embodiment] Hereinafter, the present invention will be specifically described. A steel sheet (processing original sheet) which is a matrix of the surface-treated steel sheet of the present invention, a galvanized steel sheet for household appliances, building materials, and automobile parts using a cold-rolled steel sheet as a base, in particular, in order to exhibit the effect of the surface treatment liquid of the present invention. Ideal for money zinc steel plate. Plated steel plate can be used galvanized steel plate road galvanized steel plate, galvanized _ Shao alloy plate, lin-iron alloy plate, series __ plate, galvanized _ Ming _ ^ alloy Further, the present invention can also be applied to the mysterious steel plate, the minerals 4 &amp; gold steel plate, the Ming dynasty and the like, but is preferably applied to the forged steel plate. The blackening resistance of the zinc steel sheet is improved, and the purpose is to add a small amount of Ni or C to the plating, or to use a solution containing an acidity of Ni, c〇, and e to make the metal of the steel sheet. Zinc steel plate. Next, the surface treatment liquid of the present invention will be described. The surface treatment liquid of the present invention is characterized in that it contains (A) the following pass 14 201219599 40U35pifl correction period: January 12, 2012 is the Chinese specification of No. 100134328, and the resin compound represented by the formula (I) is not corrected. (B) a cationic urethane resin emulsion, (C) one or more decane couples having at least one reactive functional group selected from the group consisting of an active hydrogen-containing amine group, an epoxy group, a fluorenyl group, and a methacryloxy group Mixture '(D) organotitanium chelate compound, (E) tetravalent vanadium compound, (F) molybdic acid compound '(G) fluorine compound and (H) water; here, relative to resin compound (A), cation The total solid content of the amine ester resin emulsion (B) and the decane coupling agent (c) {(A" + ❹ (Bs) + (Q) 丨, the solid content of the cationic amine ester resin emulsion (B) (Bs ) is 0.10 to 0.30 by weight ratio [(Bs) / {(As) + (Bs) + (Cs)}]; relative to resin compound (A), cationic amine ester resin emulsion (B) and decane coupling agent (c) solid content total amount {(As) + (Bs) + (cs)}, decane coupling agent (c) solid content (Cs) by weight [(q) / {(As) + (Bs) + (Cs)}] is 〇.6〇~〇85; 钛 偶 coupling agent relative to the titanium equivalent amount (Dt) of the organic titanium chelating compound (D) The solid content (Cs) of (c) is 50 to 70 in terms of a weight ratio {(heart) / (11^1)}; 1 is a titanium equivalent amount (Dn) with respect to the organic titanium chelate compound (D), The tetravalent hunger compound (E) is converted to a weight ratio ((Εν) / (DTi)) of 0.30 to 0.50; V is relative to the resin compound (A), cationic urethane resin emulsion (8) And the total solid content of the decane coupling agent (c), KAs) + (b) + (Cs)}, and the amount of molybdenum (Fm) of the molybdenum compound (F) in terms of weight ratio Sf / {(As) + (Bs ) + (Cs)}] counts as 〇〇〇3~〇〇3; M〇15 201219599 40035pifl Revision date: January 12, 2012 is No. 00134328 Chinese manual without scribe correction relative to resin compound U) And the total solid content of the above-mentioned _ sub-(4) resin emulsion () and the above-mentioned Wei coupling agent (c) {(AJ 0.1 ; + jB) + (Cs)}, the amount of the fluorine compound (6) converted (6) Than [(GF)/{(As) + (Bs) + (Cs)}]t^〇.〇i~ and, pH The value is 4 to 5. [Chemical 4] OH In the formula (1), Y1 &amp; Y2 bonded to the benzene ring are each independently a gas atom, the following formula (8) or the z group represented by the formula (m), and the number of substitutions of the z group per one benzene ring The average value is 〇2~丨〇. n represents an integer of 2 to 50. Here, the average value of the substitution number of the z-group means a value obtained by dividing the number of oil z-introductions by the total number of benzene rings (i.e., 2η). On the first day of the present invention, the second choice of ruthenium is used as JbYrL, and the resin compound (4) has a primary amine, a tertiary amine group, and an ammonium ionic functional group, which is the acidity of the object in the invention (ρ Η 4 ~5) The surface treatment liquid can be 201219599 4UU3^pifl for the first side of the 34328 correction period: January 12, 2012 ~ Yangshao. :solution. Further, in the present invention, when the average degree of polymerization 11 is set to be less than 2, the effect of imparting corrosion resistance is insufficient, and the other formula: It = 5 〇 is in the treatment liquid due to water solubility reduction, thickening, and the like. The stability is lowered, so that storage stability becomes insufficient. [Chemical 5] *oh2-n; r2 (II) [Chemical 6] ►CH + /R3 Κδ A' (ii η ^ (where n1 and R1, R2, R3, R4 and R5 are independent of each other to represent hydrogen atom, carbon a calcination group having a number of 1 to 10 Å or a light fluorene group having a carbon number of 丨 to η. When the carbon number of the aryl group or the base group is more than 10, the resin compound (A) cannot be sufficiently dissolved in water. The medium becomes unstable and cannot be applied. Specific examples of Ri, R2, R3, and R4 include a mercapto group, an ethyl group, a propyl group, a butyl group, a hydroxyethyl group, a 2-hydroxypropyl group, and a hydroxyisobutyl group. /, soil A- represents a helium ion or an acid ion. Specific examples of the acid ion include an acetate ion, a phosphate ion, a citrate ion, etc. 17 201219599 40035pifl is the Chinese manual of No. 100I34328 without a sizing correction date : SOU Θ 12 The resin compound (A) represented by the formula (I) is a bisphenol-formic acid condensate, and the synthesis method thereof is not limited, and for example, formaldehyde and an amine can be acted upon by the presence of a base catalyst. Obtained from bisphenol A. The cationic amine ester resin emulsion (B) in the surface treatment liquid of the present invention is only required When at least one cationic functional group selected from the group consisting of a primary amino group to a tertiary amino group and a quaternary ammonium salt group is used as a cationic functional group, the polyol, the isocyanate component and the polymerization method which are constituent monomers are not The cationic functional group may, for example, be an amine group, a methylamino group, an ethyl group, a dimethylamino group, a diethylamino group, a trimethylamino group or a triethylamine = as long as It is not limited to a primary amino group to a tertiary amino group or a quaternary ammonium salt group. The cerium coupling agent (c) in the surface treatment liquid of the present invention is as long as it has an amine group ring selected from the group containing active hydrogen. The one or more decane coupling agents of at least one of the reactive groups of the oxy group, the fluorenyl group and the decyl propylene methoxy group are not particularly limited. Particularly preferred is a tri-oxygen oxyselicin having three oximes. As a specific example, Ν-(aminoethyl)-3-aminopropyltrimethylhydrazine, 3-aminopropyltrimethoxywei, 3_epoxytonylpropyltrimonate , 3-glycidoxypropylmethyldimethoxy (tetra), 2_(3,: hexyl)ethyltriethoxy Wei, 3• Wei-propyl propyl sulfoxide is an organic titanium chelating compound in the surface treatment liquid of the present invention (D = titanium keto ketone, titanium octyl glycolate, tetraethyl butyl acrylate, titanium acetate, etc.) Titanium, titanium sulfate, titanium acetate 'titanium phosphate, and titanium strontium inorganic salts cannot be stably dissolved in the present invention, 18 201219599 40035pifl is the 10th GI34328 Chinese manual without a slash correction. Amendment date: 2Qi2 January η It is not preferable because the effect of improving the corrosion resistance is not exerted on a daily basis. Further, when the organic titanium chelate compound is dissolved in water and used, the titanium is dissolved in the form of a chelate complex, so it is preferred not to add the A highly polar water-soluble solvent or peroxide that affects the complex. The tetravalent vanadium compound (£) used in the surface treatment liquid of the present invention is not particularly limited, and specific examples thereof include vanadium sulfate, vanadium dichloride, vanadium phosphate, vanadium oxalate, and vanadium acetylacetonate. Pentavalent vanadium compounds are highly water soluble, Therefore, since the dissolution property from the film is also high and the effect of improving the corrosion resistance is small, it is not used in the present invention. Further, as the tetravalent hunger compound used in the surface treatment liquid of the present invention, the hunger compound which produces V 〇 2+ ions is high in the effect of improving the durability of the hunger compound. The molybdic acid compound (F) used in the surface treatment liquid of the present invention has no special purpose, and specific examples thereof include: sincerity, lysine, sodium sulphate, sodium sulphate, indium _, cans, and Can be linalic acid, turn 3, __ and so on. In the present invention, it is preferred to use one or more selected from the group of the compounds. One has the following characteristics: adding a fluorine compound to the surface treatment liquid) as a resistance to improvement. Here, specific examples of the gas compound (6) include an acid such as hydrofluoric acid, hydrofluoromonic acid, hydrofluoric acid, hydroquinone or hydrofluoric acid, and salts of the acids. In the present invention, it is preferred to use one or more selected from the group of fluorine compounds. In the surface treatment liquid of the present invention, the cationicity of the solid-cationic amine fat-transferring emulsion (8) and the Wei coupling agent (c) with respect to the resin compound must be determined to be the total amount of KAJ + (Bs) + (Cs)}. 19 201219599 40035pifl Revision date: January 12, 2012 is the Chinese manual No. 100134328. The solid content (Bs) of the amine ester resin emulsion (B) is set to the weight ratio [(bs) / {(As). ) + (Bs) + (Cs)}] counts as o.io~〇3〇. When the weight ratio is less than 0.10', the ratio of the amine vinegar resin is too small, and the corrosion resistance, heat resistance, and storage stability of the surface treatment liquid in the bent portion are deteriorated. On the other hand, if the above weight ratio exceeds 0.30, the solvent resistance is inferior. More preferably 〇12~〇28. Further, in the surface treatment liquid of the present invention, it is necessary to measure the solid content of the resin compound (A), the cationic amine vinegar resin emulsion (8) and the decane coupling agent (c) {(As) + (BJ + (Cs) The solid content (Cs) of the aspartic coupling agent (c) is set to 〇6〇~〇85 by weight KAS) + (Bs) + (Cs)}. If ‘=, at 0.60, the solvent resistance is poor, and if the above weight ratio exceeds 〇85, the storage stability of the surface or the treatment liquid is lowered. More preferably, in the 395 liquid, the decane couple component (6) of the titanium (DTi) relative to the organic «combined" is set to a weight ratio Kc two (the solid is poor, if the upper = the amount ^ = ^ The coating property of the stability_stability is lowered. It is preferably 55 to 65. The respective properties are high, and after the degreasing, the weight (c) of the solid component for calculating the weight ratio of the present invention is, ' Wei coupling agent (C) II, dissolved in the water, the oil produced by hydrolysis, the majority of the hydrolysis treatment liquid of the present invention is coated and dried to form the skin 20 201219599 40035pifl : January 12, 2012 is the number 100134328 Chinese _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The hunger-changing amount (Ev) of the tetravalent hunger compound (e) in the amount of titanium (〇Ή) is set to 〇3〇 to 〇5〇 in terms of a weight ratio (Εν/Ι&gt;π). If the reset ratio is less than 〇.3〇, the margin is poor. If the above weight ratio exceeds 〇·5〇, the coating property after degreasing is decreased. Preferably, it is 〇35~〇48. In the surface treatment liquid of the present invention, the solid content of the resin compound (Α), the cationic amine vinegar resin emulsion (Β), and the decane coupling agent f is combined. AS) + (Bs) + (Cs)} The amount of indium (Fm.) of the acid compound (7) is set to be expressed by the weight ratio [(Fm.) / {(As) + (Bs) + (cs)}]). 〇003 to 0.03. If the weight ratio is less than ^003, the blackening resistance is poor. If the weight ratio exceeds G, the storage stability of the surface treatment liquid cannot be obtained. In order to obtain higher resistance, it is preferably 〇·〇% or more. In the surface treatment liquid of the present invention, the total amount of the solid component is {(As) + (A) ^匕 with respect to the resin compound jA), the above heterogeneity, the Wei (B), and the Shangcai coupling. The gas conversion amount (Gf) of the compound (6) is set to a weight ratio [= storage stability of the treatment liquid = mouth sweat resistance, preferably 0.07 or less. The surface treatment liquid of the present invention in the middle of the text will be 卩; ^ - less than 4, the target 6 is careful, the β is the second value, and the value is 0 5 ° right pH value, ^ the treated layer of the galvanized steel sheet The dissolution of zinc 201219599 40035pifl The revised period: January 12, 2012 is the Chinese manual of No. 100134328 without a slash correction. On the other hand, if the pH exceeds 5, the stability of the surface treatment liquid cannot be obtained. Here, the acid agent to be used when the pH is adjusted to 4 to 5 is preferably a ketone, a formic acid, a hydrofluoric acid, a fluoride or the like, and a strong acid such as sulfuric acid, a nitrate or an acid. The original purpose is that if the sulfuric acid or secret, it can be seen that the positive value of the positive value due to pH shock (local and rapid pH change), the cation hope or the positive material on the surface of the job towel into a defect, and The salt formed therewith has a high dissolution property, resulting in a decrease in financial touch. Acetic acid 'citric acid' is a weak acid and is therefore suitable for pH adjustment. Further, since these acids are volatilized during drying of the chemical agent of the present invention, and the residual amount in the film is small, the performance is reduced even if it is excessively added, and in this respect, it is preferable. When the pH value is too low, when the pH value is adjusted to 4 to 5, the (4) secret agent is preferably ammonia or an amine having a boiling point of 1 〇〇C or less. Further, when a strong alkaline agent such as NaOH or hydrazine is produced, a gelation may occur due to a pH shock similar to that of the strong acid agent, so that it is not preferable to use NaOH or KOH. θ The water (Η) used in the present invention is preferably a resin compound (Α), an ionic amine-fat emulsion (8) 'Wei coupling agent (C), an organic titanium chelate compound (9), and a component for adjusting pH. The value of the acid component or the component of the test is less. For example, the Mg, Ca, and Si specific increase component contained in water as an impurity may lower the solubility or dispersibility of the resin compound (A) or the cationic amine lysate emulsion (8) of the present invention, resulting in generation of 5 ha The condensate of matter is not good. In addition, Na or C1 contained in water as an impurity remains in 22 201219599 4U035pifl Correction period: January 12, 2012 is No. 100134328 Chinese manual, no scribe line correction in the case of the film The remaining property is lowered, or the coating adhesion is lowered. Therefore, the water (8) to be used preferably has less impurities, and preferably has a conductivity of less than 100 pS/cm, more preferably 5 〇p/cm or less, and still more preferably 10 pS/cm or less. Further, the solid content concentration of the surface treatment liquid of the present invention is preferably 4% by mass to 2% by weight based on the solid content concentration at which HOt: is dried for 2 hours. The reason for this is that 1 the solid content concentration is 4 wt% 〇〇 "The present hair P can be lubricated on the surface of the protective film. δ rat, W) is better (W) is preferably as follows Too 4 component (WJ is formulated relative to the tree: solid resin emulsion (8)_body (4) and cationic amine ratio [(ws) / {(As) + (B ) , {( ARecalling content of AJ + (Bs)} is 0.2 or more, and then / § 10' is 0.2 to 0.4. If the above content is set to 润滑4 ^, the lubricity required, on the other hand, economical Advantageously, the raw material 3 is not allowed to ensure lubricity, and is preferably reduced to 0.4%. Preferably, it is preferably 0.3. The wax used in the present invention is at least one of the defects of the TC. Specific examples of TC oxidized polyethylene soil and polypropylene backing can be exemplified by polyglycoside, micro-microfiber, etc. If the melting point is 7〇t or more 23 201219599 40035pifl is the 100134134 Date of revision: On January 12, 2012, the required lubricity will be obtained. If the melting point is set to 12 〇, it will obtain a hard film. The desired lubricity is obtained. The butterfly (W) is preferably an emulsion which is stably dispersed in water by an emulsifier, and has a particle diameter of preferably 0.08 to 0.3 (4). If the particle diameter is _ 5 or more ' The effect of the required lubricity can be obtained, and the amount of the additive to be used is not used, so the alkali resistance or the coating property is not lowered. If the other aspect is set to 0.3 - or less, the accounting It is preferable that the floating portion in the treatment liquid is low in the specific gravity of the butterfly because the specific gravity of the butterfly is low, and it is preferable. In the surface treatment liquid of the present invention, it is considered to be an agent or a wetness (4). Defoaming__ There is no particular limitation. For example, ί uses Grease: an acid-based emulsion type, etc. The so-called wettability improvement = 曰 surface tension, an additive for galvanizing steel, &amp; phase uniformity. Water-based solvent such as ethanol, tert-butanol, butyl solute, etc.; = solution = promotion _ and j-heart effect, so (four) is suitable. The invention of the money management, can also add nickel nitrate, quarantine and other mixed salt to enter - Steps make the resistance change. =Calculate the tree to produce a pH shock, but the pasteate is produced using the above surface. A method for producing a plated steel sheet of a liquid and a method for producing a secret-coated steel sheet by the method for producing the same are described. In the case of using the surface-treated liquid of the present invention to form a surface-treated film on a steel sheet, the surface treatment liquid is applied to the weave. On the steel plate, 24 201219599 40〇35pifl Revision date: January π, 2012 is the 100113134328 Chinese manual without a scribe line correction, the temperature is 5G ° C ~ 18Gt for drying, forming a single side of the mother on the surface of the steel plate The amount of adhesion was 〇2 g/m2~(8 g/m2 of the surface treated film. (2) At this time, if the adhesion amount per one side of the surface treatment film is less than 〇2 g/m, sufficient corrosion resistance cannot be obtained, and on the other hand, if the adhesion amount per one side of the surface treatment film exceeds 1.8 g/m2 The effect of the amount of adhesion is saturated, and it is not economically disadvantageous and the coating property is lowered. Therefore, the adhesion of each single side is not determined to be 〇2 g/yM 8 g/m2, preferably 〇3 coffee 2 〇 〜g/m2 ' more preferably 0.4 g/m2 to 1.4 g/m2. As a method of applying the surface treatment liquid of the present invention to a plated steel sheet, it is known that a coater (three-roll method, two-way method, etc.), a squeeze coater, a die coater, and the like are known. Any method. In addition, it is also possible to adjust the coating amount by the air knife method or the extrusion method after the coating treatment, the immersion treatment, or the blast treatment using a 摈t coater or the like, and the appearance is uniform: thick Homogenize. / Applying the surface treatment liquid of the present invention (Caf (4)) to the plated steel sheet 彳4, and heating the wire without touching the water. The dry structure can be used, human fans, hot air ovens, high frequency induction heating furnaces, infrared furnaces, and the like. As stated above. Drying is to adjust the plate temperature of the plated steel plate itself to 5 〇 it ~ 180C seam. If the board temperature is lower than 5 (). (3) The more the towel 2: The contact resistance becomes insufficient. On the other hand, if the plate temperature is reached = the corrosion is reduced. * The present invention having a surface-treated film formed by the above method can also be applied to a resin film on its surface to obtain a higher 25 201219599 40035pifl Revision date: January 12, 2012 stomach stomach In the Chinese Patent Specification No. 1QG134328, the surface-treated coating formed by the surface treatment liquid of the present invention may be applied to one side or both sides of the plated steel sheet. The effect of the present invention will be described. It is presumed that the components of the surface treatment liquid towel of the present invention are as follows, but the present invention has any limitation. In the surface treatment liquid of the present invention, the resin compound (A), the cationic amine vinegar resin emulsion (8), and the Wei coupling agent (6) are main components, and the skeleton of the film is formed by these main components. The surface treatment liquid containing the resin compound (A) having a cationic functional group (the above formula (π) or the formula (ΠΙ)) is adjusted to a weakly acidic value, whereby the surface treatment liquid increases stability, And ensure storage stability. Further, by imparting cationicity, the resin compound (A) is insoluble in an alkali solution and becomes a film having testability. Further, by selecting the double-presence as the skeleton of the resin compound (A) (IV), it is difficult to dissolve in a polar solvent (the imparting of solvent resistance), and the adhesion and corrosion resistance are improved. However, the above-mentioned resin compound (Λ) tends to have a yellow color (resistance, a decrease in yellowing) by heating and becomes a hard film. Therefore, in the present invention, by formulating the cationic urethane resin emulsion (B), the hardness of the phenol resin is moderated, and the resistance of the processed portion is ensured. The cationic amine ester resin emulsion (B) has the above effects, but on the other hand, the film is easily peeled off with respect to the polar solvent. Therefore, in the present invention, f ensures (solvent resistance to a polar solvent) and yellowing resistance as the target X, and sings the sulphur coupling agent (c). Shi Xiyuan coupling agent (c) due to the end of the burning of oxygen 26 201219599 40035pifl is the 10013434328 Chinese manual without a slash correction This revision period: January 12, 2012, the base hydrolysis to produce active Wei alcohol (Si_〇H ), so there is an increase in the adhesion between the secret and the original material (lin layer) or the upper coating _QpeGating. Further, a part of the stone is dehydrated and condensed to produce a decane bond (1-0 'the oxime bond is continuously polymerized (polyoxyalkylene. -Si-οιοι). Thereby, it becomes an extremely stable structure. It can be used for the corrosion resistance, solvent resistance, and yellowing resistance of the skin. ❹ 3 This can be considered as 'by using a resin compound (4) which is a main component at the surface in an appropriate ratio, a cationic amine vinegar resin emulsion (8), :堇C) 'A variety of properties can be obtained with a good balance. However, in the case of a component, it is impossible to obtain a solution to the previous problem and the solution. Therefore, in the surface of the present invention, the resistance of the organotitanium chelate compound (D) is improved and high, and the degreasing (8) is regarded as a drip, and the above is based on the amount of the Wei coupling agent. : Chelate compound (9). So when the skin = time chelate = its excess content, (four) (four)) decline 'can not be obtained after storage and before storage 27 201219599 40035pifl Revision date: January 12, 2012 for the ugly 3 - text Say the same quality as day ____. Act as a rot 1_ coffee (tH (4) minus compound (5) a and two Γ (such as the pure state of the word). Special oxygen _ child [v〇, in a humid environment It is difficult to dissolve in the next: In the film, the effect of the inhibitor is exhibited, so it is presumed that even if the number of r = strong processing such as bending, the surface treatment film or ==. two T: r: Ming; Or the skin model bone of the _r sub-functional group ===== as an essential component. Excellent blackening resistance is obtained in the acid compound (7) of the present invention. The zinc-acid compound (7) gas (smelting) is irrelevant to produce ore. Type of application (electricity = or increase the mining and raw materials (iron;:::: and = high wealth or A1, The plating of the metals in the ore zinc is followed by the addition of Mg to blackening, which becomes darker. It is also known that the surface treatment of 1 ^ or the surface of the plating is tempered and the blackening resistance is lowered. Right to improve the white rust deoxidation of the mineral zinc, the process of converting zinc oxide into the form of zinc oxide formed on the surface of the anoxic zinc oxide is not fully supplied with oxygen. 5 Go due to corrosion in zinc (oxygen oxide type zinc oxide It is black. ', Oxygen-deficient zinc oxide, the cause is high, the phenomenon of blackening under the condition is deprived of oxygen, converted into anoxic oxidation-generated zinc oxide) 28 201219599 40035pifl Correction Date: January 12, 2012 is No. 100134328 Chinese manual without underline repair ^ In the present invention, by introducing a molybdic acid compound into a surface treatment film, excellent blackening resistance can be obtained. It is a transition metal: an oxide of Mo〇2 and M〇〇3 is bonded to oxygen. Further, there is a molybdic acid (MoO) bonded to oxygen. Therefore, in the present invention, it is considered that molybdenum is used.酉夂(=〇04) is divided into two temperatures and high humidity or rot The lower layer is converted into an oxide of molybdenum (such as Mo〇3) to appropriately supply oxygen and zinc oxide to the surface of the zinc plating. The inventors have estimated that the suppression of blackening is obtained by the machine system. Further, the surface treatment composition (6) of the present invention is an essential component. The prior art is caused by the fact that the addition of the gas compound (G) is excellent in the case where the steel plate is connected to the touch plate. Although the mechanism of human sweat adhesion has not yet been clarified, it becomes black and oxidized and becomes rot. _==^ People's sweat (weakly acidic) is affected by ° and it looks like a color. The surface of the galvanized electrode grows slowly, and the effect of adding Zn, A1, and Me1 on the surface of the zinc surface of the _ surface ^==_ compound (6) becomes stable on the surface of the plated steel sheet, so that the surface layer can be stabilized. Such as poorly soluble compounds, plating; ionized chlorine acid or its salt is particularly easy to form. 7 The effect of improving the sweat is large, so the resin compound (A) of Table 1 (Table la and Table lb) is not compared with the example. Table 2 29 201219599 40035pifl is the i_28 幌 duck without _ positive test date: Congnian The cationic amine ester resin emulsion (B) shown in the month 12, the oxime coupling agent (C) shown in Table 3, the titanium compound (9) shown in Table 4, and the "(E), Table 6 shown in Table 5) The indium acid compound (7) shown, the gas compound (G) shown in Table 7, and the wax (W) emulsion shown in Table 8 were appropriately mixed to prepare a chemical solution. In addition, the Ronglin steel sheet shown in Table 9 was used as a processing original plate. For example, the surface treatment liquid of the example is prepared in such a manner as to be in the composition of Tables 1 to 4 to Table 12, and is adjusted to the pH value of Table 12-2 by using acetic acid and ammonia, and then under n〇t. When 2* is dried, ^^ is closed to 1G secret (4) It is adjusted by deionized water, and the solid concentration is set to be 'the above deionized water is a plating using conductivity as a dry bomb. The touched surface is subjected to inspection and removal, and the surface is treated with water on one side without water washing, and the surface treatment liquid is plated with steel. Single = Table 1 and speed; ;:===: The amount of the second agent is divided into the amount of adhesion. The amount of the S1 adhesion is converted into the film surface treatment liquid and the quality of the forged steel plate produced (planar part 30 201219599 40035pifl is the first face of the Chinese version) Rilin _ line correction this fine period: Li Nian 丨 日 日 and f touch, bending processing section + sex, financial discoloration, resistance to sputum after application of alkali degreasing, blackening storage stability, resistance × = applicability after degreasing, solvent resistance, and 14 in each test. The results are shown in Table r, and the evaluation of the properties is performed under the following conditions: (1) Planar part Corrosion resistance Each sample was subjected to a salt spray test (JIS_Z_23, after 12 hours, the white traitor; ^. rust generation area ratio was evaluated. The evaluation criteria are as follows. 〇◎• White rust generation area ratio 〇% :+: white The area ratio of rust generation is less than 5%. 〇: The area ratio of white rust is 5% or more and less than 10%. 〇-: The area ratio of white rust is 10% or more and less than 20%. △: The area ratio of white rust is 20〇/〇. Above, less than 4〇% x · White rust generation area ratio is 40°/. or more (2) Resistant to the bent part Each sample was sandwiched between rods of 2 mm in diameter (made of non-mineral steel) and squeaked, and tightened with a vise. The bent sample was subjected to a sleeping U-fog test (JIS_Z·2371-2000) to pass 72 The area ratio of white rust generated on the outer (outer) side of the hour is evaluated. The evaluation criteria are as follows. ◎: The area ratio of white rust generated in the bent portion is 〇% 〇+: the area ratio of white rust in the bent portion is less than 5% 〇 : Bending processing part (5) White rust generation area ratio is 5 〇 / 〇 or more and less than 1 〇 % : The area ratio of white rust generated in the bent portion is 1% or more and less than 40% ' △: White of the bent portion The area ratio of rust generation is 4% or more and less than 201219599 40035 pifl. Correction date: January 12, 2012 is No. 100134328. The Chinese manual has no scribe line 80%. X: The area ratio of white rust in the bent portion is 80% or more (3 The rice resistance after degreasing was dissolved in pure water with an alkali degreaser CL-N364S (manufactured by Parkerizing Co., Ltd.) at a concentration of 20 g/L, and heated to 6 (rc). Each sample was immersed in a solution test towel; after 2 minutes, it was taken out, washed with water and dried. Each sample was subjected to a salt spray test (JIS_z_2371_2〇〇〇), and the area ratio of white rust generation after 72 hours was evaluated. The evaluation criteria are shown in the price of the above (1). (4) Blackening resistance Each sample was allowed to stand in a constant temperature and humidity machine controlled to a temperature of 8 (rc, relative humidity of 95%) for 24 hours, at which time the brightness (l value) was changed (AL = test) The latter L value is calculated from the value of 1 before the test. The evaluation criteria are as follows. The L value is the SR2 制造 manufactured by Nippon Denshoku Industries Co., Ltd., and the specular component (excluding specular reflected light) Measured. ® · -6^AL 〇: -10$AL&lt;-6 △ : -14$AL&lt;_10 x · AL&lt;-14 (5) Heat-resistant discoloration Each sample was placed in an infrared induction furnace at 3〇 After heating to a plate temperature of 50 ° C for a second, after 30 seconds, visually observe the appearance of the surface when it was naturally cooled to room temperature. The evaluation criteria are as follows. 32 201219599 4UUi5pifI is the Chinese manual of No. 100134328 without drawing [j-line revision Corrected flood season: 2〇12年i月12日◎: No discoloration 〇: very light brown △: pale brown x: brown (6) coatability applied to each sample as melamine alkyd Deiicon (registered trademark) #700 (manufactured by Otsuka Paint Co., Ltd.) for coating, calcined at 13 ° C 0 30 minutes, after forming a film with a film thickness of 30 μm, and then immersing it in boiling water for 2 hours, and immediately into the cut of the steel that reaches the square (10 "one, 1 mm interval"). In the Erichsen extruder, 5 mm of the dicing process was performed so that the cut portion became the outer side, and the peeling area of the coating film was measured by the tape. The evaluation criteria were as follows. Further, Erichsen squeezed The pressing condition is set to a punch diameter of 20 mm, a die diameter of 27 mm, and a press width of 27 mm in accordance with JIS-Z-2247-2006. ◎: no peeling: peeling area is less than 3% 〇〇: peeling area is 3% or more and less than 10%: the peeling area is 10% or more and less than 20% Δ: the peeling area is 20% or more and less than 50% x: the peeling area is 50% or more (7) The coating property after alkali degreasing is performed The same alkali degreasing as in the above (3) was carried out, and the same coating test as in the above (6) was carried out on each sample. The evaluation criteria were also the same as in the above (6). (8) Solvent resistance 33 201219599 40035pifl Revision date: 2012 On the 12th of the next month, the Chinese version of the "No. 100134328" "Mauze gauze" A load of 4.90 n (50f) A is pressed to the surface of each sample, in order to spread the charge ^ frictionally rubbing mesh fiscal Assessment Comment county registration marks as human ◎:... Traceless. . 〇+: No traces are observed when viewed from above, but a slight permission is allowed when tilting. . From the time of the money, the traces of the judgment are obviously 可-- when the angle is observed, the trace is allowed to be seen. △: Obvious traces were observed when viewed from above. x · Film peeling. (9) Storage stability The surface treatment liquid of the table * is applied to 4Q. The evaluation criteria are as follows. ◎: No change 3〇天. The appearance of each surface treatment liquid was visually examined and evaluated. Or the viscosity is slightly higher or gelatinized 〇: a very small amount of smear is visible △: visible trace killing, X: a large number of smothers are visible, (10) sweat resistance is prepared for oak, and the surface is added according to Jls μί, Press the light rubber stopper on the artificial sweat of 1-1995. The second = part 'production - the area of the period, the temperature of the humidity _ the temperature of the strange = = for the temperature of the fast after the quiet for 4 hours, the evaluation, 34 201219599 40035pifl for the l·34328 Chinese reward book without Line correction This revision date: Appearance changes in the parts of the U-day sweat contamination of the U-day. The evaluation criteria are as follows. ◎: No discoloration 〇: Very slight discoloration △: slight blackening x: obvious blackening (11) Lubricity A disc-shaped test piece having a diameter of 100 mm was cut out from each sample to have a head diameter: 50 mm The mold diameter is 51.91 mm, and the blank holder force (blankholder pr'ssure) ==it (ton) is formed into a cup shape. The appearance of the extruded surface (outside of the side of the cup) of the molded article was visually examined to evaluate the degree of damage and the degree of blackening. The evaluation criteria are as follows. ◎: The whole surface is almost unchanged, the appearance is uniform 〇+: The blackening is slightly slightly generated, but the appearance is uniform 〇: slight damage and blackening occur, and the appearance is obviously uneven: local damage and blackening, appearance Significantly uneven △: The damage and blackening occurred sharply around the corners. χ: Cannot be formed and damaged. 35 201219599 40035pifl No. 100134328 Chinese manual without slash correction This revision period: January 12, 2012 [ Table la] Table la resin compound (A) No. Y1 Y2 The average value of the substitution number of the Z group η Z group: Formula (II) Z group: Formula (II) R1 R2 R1 R2 A1 Hydroquinoneethyl 0.4 5 A2 ethyl mercaptohydropropyl 0.7 3 A3 ethyl propyl hydrogen ethyl 0.4 10 A4 transylethyl hydroxyethyl hydroxyethyl transylethyl 0.5 5 A5 -C12H23 methyl hydrogen hydride 0.5 5 A6 - C12H22OH Methylhydrogen hydrogen 0.5 5 A7 Hydrohydrohydrofurylethyl 0.1 5 A8 Hydrogen hydrogen methylethyl 1.2 5 A9 Hydrogen hydrogen methyl ethyl 0.4 80 * The group represented by the formula (Π) is used as the Z group. [Table lb] Table lb Resin Compound (A) No. Y1 Y2 The average value of the substitution number of the Z group η z group: General formula (III) Z group: General formula (III) R3 R4 R5 R3 R4 R5 A10 Hydrogen hydroquinone Methyl ethyl methyl group 0.4 5 All ethyl methyl hydrohydropropyl hydrogen 0.7 3 A12 ethyl propyl methyl hydrogen ethyl fluorenyl 0.4 10 A13 hydroxyethyl benzyl ethyl hydrogen via yl ethyl hydroxy Base nitrogen 0.5 5 A14 -c, 2H23 methyl hydrogen hydride 0.5 5 A15 -c12h22oh methyl hydrogen hydride 0.5 5 A16 hydroxyethyl hydroxyethyl hydrogen hydroxyethyl hydroxyethyl hydrogen 0.1 5 A17 Hydroxyethyl hydrogen thioethyl hydroxyethyl hydrogen 1.2 5 A18 Hydroxyethyl hydroxyethyl hydrogen hydroxyethyl hydroxyethyl hydrogen 0.5 70 * The group represented by the formula (Π) is used as the Z group. 36 201219599 40035pifl is the Chinese manual of No. 100134328. There is no slash correction. The date of this revision is: 2〇12年12月12曰[Table 2] Table 2 Amine ester resin (B) No. Amine ester resin (B) Ionic Γ.. ...........^^ Manufacturer One^B1 Adeka Bontiter HUX-670 Cationic ADEKA (li)_____ B2 Superflex 600 Cation First Industrial Pharmaceuticals - One B3 UC-20 Cation = Ocean Chemical Industry ( Stock ___— B4 Adeka Bontiter UX-206 Non-ionic ADEKA (share) B5 Hydran AP-10 Anion DIC (stock) [Table 3] Table 3 decane coupling agent (C) No. .........矽垸 coupling agent (c) Cl --3- 3-mercaptopropyl=methyl decyl decane C 2 amide ethyl) _ 3-aminopropyl trimethoxy hydroxy hexane C 3 3-glycidoxy propyl trimethoxy Baseline C4 3-mercaptopropenyloxypropyltrimethoxycarbane C5 Vinyltrimethoxymethane [Table 4] Table 4 Titanium Compound (D) No. Drinking Compound (D) D1 Acetylpyruvate Titanium (Ti: 12.5 wt%) D2 Titanium tetraacetate pyruvate (Ti: l〇.8 wt%) - D3 Titanium nitrate (Ti: 16.2 wt%) D4 Fluorotitanic acid ((Ti: 29.2 wt%)) [Table 5] Table 5 Vanadium compound (E) No. Vanadium compound (8) El vanadium ruthenate (v: 32_9 wt%) - E2 Ethyl vanadate pyruvate (V: 19.2 wt%) E3 Vanadium sulfate (V: 31.2 wt%) E4 Ammonium metavanadate (V: 43.5wt%) 37 201219599 40035pifl No. 100134328 Chinese manual No underline correction This revision period: January 12, 2012 [Table 6] Table 6 I acid compound (F) No . Key acid compound (F) FI Na2Mo〇4*2H20 F2 fNH4') fiMo7〇24-4H20 F3 (ΝΗ4)3ΓΡΜο1204η1·3Η20 [Table 7] Table 7 Fluorine compound (G) No. Fluorine compound (6) G1 Hydrofluoric acid G2 Hydrofluoric acid G3 Hydrofluorotitanate G4 Acidic ammonium fluoride G5 1 Na[Table 8] Table 8 Wax @0 Emulsion No. W1 _ Wax type (W) Melting point (°c) Solid content of the dispersion (Wt% Particle size (μηι) Gasified polyethylene wax 115 20 0.1 W2 Microcrystalline wax 90 20 0.1 W3 One paraffin 50 20 0.1 炊 A product obtained by forcibly milking the above wax with an emulsifier. [Table 9] Table 9 GF2 GF3 GF4 GF5 —— Processing original plate (mineral plate) __ J^jAg_Zn-5.0 mass % Al-0.6 mass% Mg-0.04 mass% Ni Hefei Zn-4.5 mass % A1-0 8 mace·»/· iUir_n ra ή 人υ mass y〇mass% Mg-0.04 mass% Ni alloy: Zn-4.5 mass % Al-0.8 mass% Mg-0.03 mass% Ni alloy: w insect!Ζι^5· 1 mass % Al-0.9 mass% Mg-0_09 mass% Ni alloy: Zn-S.〇mass % Al-0.5 mass% Mg alloy steel plate, school r· ^ Γ7~Τ~:~:~~:- ※ plating mass % A1 alloy steel plate is t, but the above indicates the amount of plating adhesion per one side. The amount of bonding is ~90 glvci ~~ 60 g/m2 90 g/m2 90 g/m2 90 g/m2 38 201219599 tnINIifl^fNloziInHI·} Tell Hrs鹱観||1 helmet 扒旮黯sze inch £1001 移脉uulsoso inch 1丨01褛】Ι-2&lt; (W) solid content% 〇o ο Ο ο ο oooo ο oooo Ο ο ο 〇0 &lt; 1 1 III \ 1 1 « 1 I 1 1 1 1 1 1 IN 〇N/ _ Η % ^ 寸 inch inch inch inch inch inch inch inch inch inch inch inch inch type &lt; δ δ S inch Ο S inch inch inch inch s inch inch inch inch inch inch inch inch inch 〇δ δ δ δ inch inch &amp; Mo conversion % MD d Ό &lt;ό Ο Ό Ο ο d ο VO 〇V〇c5 ο ο ό dodo νο ο VO ο Ο Ο &lt; CN CN 13⁄4 CN S CN Uh (N &lt;N Ph CN (3⁄4 CN Χ. (Ν Ν IX. (S Uh iS &lt;N ϋ. &lt;Ν cs CN ω V conversion 1 inch d寸 inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch size size size size size size size size size size size size size size size size size size size size size size size size size size size size size size size size size size size size size size ω m ω iS ω CN ω Q Ή1-H ^—Η »*Ή i—Η 1.134 1 1,134 ϊ-Η Type inch 1-HQQ »-Η Q 1—Η Ρ 1—Η Q iH Q 1—HQ s inch P * - Η QQ inch Q inch Q inch QQ CN Ρ »—Η Q D1 : D4 u 1$峒§ § δ § 00 νη v〇ir&gt; § sss W) SSS § Type m U υ ^-Η Ο »·~Η ο U uu T uou UU C2 : C3 =1 : 1 rj ΰ GU /-*N CQ N—^ Solid content% ο σ&gt; CN CN a\ / CN VO »—H VO v〇o &lt;〇ν〇F· Η Os *-Η fN m CQ 1—^ PQ ι—Η m CQ PQ 1—H PQ 1-H PQ PQ OQ CQ Ξ Ξ S ft) »-Η CQ PQ /~N &lt; Solid content ο 寸 ϊ&quot;Η »/Ί Ο ID dd inch inch inch 〇 \ (N ON (N inch inch inch purple! View C 1-^ C »-Η CC ccl—( &lt;&lt;&lt; ϊ &quot;Η &lt; 1-^ &lt;&lt;&lt; iH CN cn &lt; C &lt; Inventive Example 1 i Inventive Example 2 Inventive Example 3 Comparison Example 1 1 Inventive Example 4 1 Inventive Example 5 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Inventive Example 6 Inventive Example 7 Inventive Example 8 Inventive Example 9 d Inch wo 00 〇\ ο (N mi· H 00 1-Η 6ε 201219599 mz IncIitl-INI 0 (N:smHIs pieces HI sacrifices_ITa 饀^-&amp;-黯scsle inch ε ι ο ο i 脉脉 ua§0 inch o ο ο ο 〇 〇〇 1 Ο 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 δ Ο s ο Ό Ο ο VO ο dv〇d ν〇dd • ο ο ο VD Ο \〇ο mdos CN Ρη tin (S 13⁄4 cs (N P-. (Ν Ρη (Ν |Χ| (Ν IX. (Ν (N CN md 0.34 1 1 0.44 1 1 0.48 1 | 0.32 I | 0.35 I | 0.46 I in o Γ °·24| 1 0.33 1 1 0.49 1 1 0.55 inch inch o (N ω ω (NW (N PJ CN w CN ω CN W (Ν ω &lt;Ν (Ν W (N P | 0.75 I 0.85 1 ψ &lt; CNj T^H 00 d | 0.88 | 1—H ι—Η o 1—H II QQ ι—Η QQQQQ iH QQQQ I-Η QQ &gt;— HQ &lt;Ν U-) 00 '«Ο CN § § § § § § S § § o 1—Η υ U u iH uu , io U υ U υ τ —Η υ u U 〇 〇 o o o Ό Ό Ό fH ν〇vo r*H PQ ι—Ι r—&lt; CQ Yin—P3 PQ i—^ PQ PQ Ρ3 1—^ CQ m CQ CQ 〇\ (Ν ^ Η inch inch inch inch inch inch inch inch iH C &lt; c &lt; CT - ^ &lt;&lt;&lt;&lt;&lt;&gt;&gt;&lt;&gt;&gt;&lt;&gt;&gt;&lt;&gt;&gt;&lt;&gt;&gt;&lt;&gt;&gt;&lt;&gt;&gt;&lt;1&gt;&gt; 13 Comparative Example 14 Inventive Example 14 Inventive Example 15 1 Comparative Example 15 Inventive Example 16 Comparative Example 16 1 σ &gt; m (N ^T) &lt;N CN 00 CN 〇\ CN r*-H m (Ν m 趑佑婪: (Mr Rong^nqm : (ο) -#4nqssnnf : (d) -#&lt;nOJKwsf : (a) ·荽伞^命镧 Filling: (α) -- GY 蓉&lt;°q&gt;ls#^ Pull. I-state Wl4y4: (V) 0 inch 201219599 斗&lt;N-0Id mtNI 哎i 壮&lt;NI 0(N: step on [Π3Ι _ speak 3! _ ffs®_ 郜饀8 (Ne inch ε i ο oi »®su-asso inch'οΐ ( X7) o Ο Ο ο 〇〇ο ο ο ο 〇〇〇ο 〇Ο o Ο ο 〇〇〇〇 (X6) 0.050 0.050 0.050 0.050 ι 0.050 0.050 0.049 0.050 0.050 0.050 0.050 0.040 0.040 0.050 0.050 ! 0.050 0.050 0.048 0.048 0.048 0.048 0.048 0.050 (X5) ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** ** 0,40 | 0.00 | 0.00 | 0.40 0.40 0.40 0.40 0.36 0.40 0.40 0.40 0.40 0.40 (X3) % § 00 v〇in 8 δ § § § in § VO S (X2) 0.75 0.75 0.75 0.75 0.73 0.70 0.68 0.75 ! 0.75 0.75 0.75 0.65 0.65 0.25 | 0.75 | 0.75 0.75 ! 0.72 0.54 0.63 0.82 0.87 0.75 (XI) 0.20 0.13 0.11 0.08 0.27 0.29 0.32 0.20 , 0.20 1 0.20 0.20 0.06 0.06 0.50 | 0.20 I 0.20 "0.20 | 0.23 1 0.23 1 ! 0.23 0.13 0.12 0.20 pH in inch. inch·in ¥ inch· yr\ inch· yrt inch · vn inch wt% ro m ro m cn mmmm ο Ο ο m cn m cn m type pro-phosphoric acid phosphoric acid phosphoric acid phosphoric acid phosphate phosphate phosphate phosphate phosphate Original phosphoric acid|Nitric acid 1 orthophosphoric acid ι 1 orthophosphate ι, orthophosphoric acid 1 orthophosphoric acid ι, orthophosphoric acid, orthophosphoric acid, orthophosphate, orthophosphate, phosphoric acid, phosphoric acid, phosphoric acid, inventive, inventive, inventive, inventive, inventive, inventive, inventive 5 Comparative Example 2 Comparative Example 3 ι Comparative Example 4 丨 Comparative Example 5 Comparative Example 6 Comparative Example 7 1 Comparative Example 8 1 Comparative Example 91 Invention Example 6 Invention Example 7 Invention Example 8 1 Invention Example 9 1 Comparative Example 10 Invention Example 10 Invention Example 11 Comparative Example 11 Comparative Example 12 d 1-Η CN cn inch 00 〇m inch in Bu-μ 00 〇\ 3 I inch 201219599 [nfNlm: a swollen zi otN: step on raHIs cover 31 hit fi destroy _ira 辗-ΜΉ -黯sfNro inch ε ι ο ο i 祗u-asso 寸ο 〇Ο 〇〇〇ο 〇〇! 0.050 0.050 1 0.050 0.050 ! 0.050 0.050 0.050 0.050 | 0.050 0.24 0.33 0.49 0.55 0.40 0. 40 oo ν〇(N ι/Ί § δ § § § 0.75 1 0.75 1 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.20 0.20 1 0.20 1 0.20 | 0.20 | 0.20 0.20 0.20 0.20 — inch · 'sf- LTi cn mmm ΓΟ mmm ro Pro-phosphoric acid 1 pro-phosphoric acid I pro-phosphoric acid pro-phosphoric acid phosphoric acid 1 orthophosphoric acid I | orthophosphoric acid | 1 orthophosphoric acid I Inventive Example 12 1 Inventive Example 13 I Comparative Example 13 Comparative Example 14 Inventive Example 14 I Inventive Example 15 Comparative Example 15 1 invention example 16 1 comparative example 16 &lt;N 〇〇CM a Ψ-* rn (N m (o) =9xAo+CQ+v) / (ij) =ςχΛρο) / (&gt;3)=inchχΑρα) / (10) =ex &lt;(lo+lm+l&lt;r) / (ιυ) =lfNx&lt;(lu+lm+l&lt;) / (1m)卩ιχ (※:! 5+&lt;d) / CM)=卜X &lt; (ο+ΐν) / 201219599 mCNIlncI Zhuang (NI ocsl: step on mHI pieces s fs 堞IraKH helmet 扒ϋοο(Νε inch ε ι ο ο i 濉 u u'alnso inch I-u&lt; (W) solid content 〇o Ο ο ο ο ο ο ο Ο Ο 1—Η οο »-Η Ο »ri Ο ο ο Ο ο ο 缌 00 1 1 1 I 1 I 1 IIII &lt; Η &lt;Ν m IIII 1 a ^ Η inch inch 1—Η ΙΤ) Ο Ο Ο τ τ τ τ τ τ τ ! ! ! ! ! ! 骚 骚 骚 骚 骚 骚 骚 骚 骚 骚 骚 骚 骚 & 寸 寸 ί ί ί CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN δ δ δ δ δ δ δ 〇Η 〇 〇 VO CN 〇 〇 〇 〇 〇 〇 Η Η Η ο ο VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO VO 1 (N [X. CN l·. CN ϋ. I (S Ρη (Ν Ρη (Ν CN CN CN 13⁄4 CN IX. CN (Ν CN CN ϋι Ξ Ξ ε Ε WV conversion inch inch inch o inch inch inch inch inch inch inch寸 inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch W CS ω CS ω rs| ω (Ν ω (Ν ω CN ω &Lt;Ν W cs ω CN W (Ν ω &lt;Ν PQ ω Ξ Ξ ω ω Ξ Q v^ Ti conversion iH ^•Η ι—Η »-Η ί-Η r—Type inch&lt; QQQ 1—Η Q Η Ο Q 1—Η Q Ρ Q 1~4 QQ f ι Η Ρ ι»Η QQ ί—Η Q ι—Η QQQQ ι—Η Ο Ρ rN u 'w/ Solid content s 8 S δ SS § § s § § § δ SSS § § S Type m 1—H oi—H Η UU υ FH υ ψ Η υ *-Η υ ι-Η υ ί ί Η Τ Η Ο Τ Η Η υ ι ι Η υ ο (4 Ο ^-4 Ο Ο , _ Η Ο ι-Η υ PQ Solid content 'sO ν〇Ό Ό ι-Η ν〇ν〇^-4 \〇\〇ν〇νο Ό «骤CN &lt; * —H PQ »—H CQ Ώ ω CQ CQ CQ m »-Η CQ PQ (Ώ 1-Η PQ CQ DQ 0Q r Η C3 CQ Ρ3 CQ »*Η CQ Η CQ c Solid content 1 inch inch inch inch inch inch inch inch inch Inch 寸 inch inch inch inch inch type 1 T—Η y-^ &lt;&lt;CC »-Η C &lt; C &lt; ^-Η &lt; C &lt; ί *»Η ί«Ή C τ-Η &lt;1 &lt &lt; 1 - Η &lt; Comparative Example 17 Comparative Example 18 Inventive Example 17 Inventive Example 18 1 Comparative Example 19 1 Inventive Example 19 Comparison Example 20 Inventive Example 20 Inventive Example 21 Inventive Example 22 Inventive Example 23 Inventive Example 24 1 Inventive Example 25 Inventive Example 26 Inventive Example 27 Comparative Example 21 Comparative Example 22 Inventive Example 28 Inventive Example 29 Comparative Example 23 Comparative Example 24 CO ΙΤί m ν〇 ΓΠ Pi 00 m CT\ m ο 5 σ\ yrt CS W-) m 201219599 mINltlcl 壮ζι 0(Ν:δξΕΠΗΓ 攀将3!举f5 挨_郜helmet«Aberdeen Issz ε inch ε a ο ο ι 移脉u-索 寸 Ο Ο Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο : Ο τ τ τ τ Ο — — — ο ο ο ο S S ο ο : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : ο inchο inch inch inch inch « WW Ξ W r—^ PQ W Ξ 1—Η WW 1—Η Γ·Ή 1—Η Q *-Η QQ ^Η QQ ^•Η Q τ~^ QQQQ § § § § δ S § § § § α Ο U Η υ U ϋ »·^ U u U υ Si tf ml m έ Ό Ό Ό Ό ΡΡ m ΡΡ Τ&quot; Μ PQ CQ &gt;—Η m ^-Η 03 τ— ^ CQ τ &quot;Η CQ *— CQ CQ inch inch inch inch &lt;&lt;&lt; τ-Η C c C ι-Η C &lt; 1-Η &lt;&lt; φ: &lt; Comparative Example 25 I Inventive Example 30 1 Inventive Example 31 1 1 Inventive Example 32 1 1 Inventive Example 33 1 Comparative Example 26 1 Comparative Example 27 1 1 Inventive Example 34 1 Inventive Example 35 i Comparative Example 28 in 〇〇IT) Os SSS s 3ί - , f η_5 - - f ^ .. 201219599 ΕίΝιΠΙ:!壮&lt;Nl otN: step on mHIS cover s 鹱観 destroy _KH helmet 扒旮黯oo (Ne inch ε ι ο ο i send «u'avoso inch bucket&lt;Ν_ΙΙ&lt;] 'Ιϊ (Χ7) ο o ο o 〇ooo Ο Ο Ο 0.31 0.39 0.31 0.25 Ο 〇〇〇〇〇〇Ο (Χ6) 0.050 0.050 0.050 0.019 0.006 0.088 0.125 0.050 0.050 j 0.050 1 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 (Χ5 ) ο 0.033 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00:00 0.40 0.40 0.40 0,40 0.40 0.40 0.40 0.40 0.40 1 0.40 1 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 (Χ3) SI § § s % § § s § ss § § § § § (Χ2) 0.75 0.75 0.75 0.75 0.75 ; I 0.75 1 0.75 I 0.75 0.75 1 0.75 1 1 0.75 1 J 0.75 | | 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 (XI) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 1 0.20 1 I 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 — IT) — — in iTi — in iTi in inch* ο cn inch inch 〇 inch · 〇υ-ϊ 〇^6 to other wt% m cn m ro cn cn m ro ro mm CO mm CO mmm type pro-phosphoric acid orthophosphate phosphate Pro-prophosphate phosphate phosphatidyl phosphate phosphatidyl phosphate | pro-phosphoric acid | pro-phosphoryl orthophosphate-phosphoric acid phosphatase-phosphoric acid phosphatase-phosphoric acid phosphoric acid Comparative Example 17 Comparative Example 18 Inventive Example 17 Inventive Example 18 Comparative Example 19 Inventive Example 19 Inventive Example 20 Inventive Example 22 Inventive Example 22 Inventive Example 23 Inventive Example 24 Inventive Example 25 Inventive Example 26 Inventive Example 27 Comparative Example 21 Comparative Example 22 Inventive Example 28 Inventive Example 29 Comparative Example 23 Comparison Example 24 Comparative Example 25 Inventive Example 30 No. m ir&gt; m P; 00 m 0\ m Ο 5 On CO ^ inch 201219599 mzi 哎i 壮 fNI 0ΙΝ: hi-fi 3Ι # 柃3!鹚flfliis _ ifa 舔«frlgooz e inch ε ΐ ο oi 濉 u u-agso inch ο Ο 〇〇oooo 0.050 0.050 0.050 ; 0.050 ! 0.050 1 0.050 0.050 1 0.050 0.0000 at 00:00, 00:00, 00:00, 00:00 0 Π | 0.40 | | 0.40 s § § § s § 0.75 1 0.75 S ; 0.75 0.75 L^75_1 0.75 J 0.75 0.75 | 0.20 Ί 0.20 0.20 0.20 1 0.20 | 0.20 0.20 0.20 in in — IT) inch _ m cn CO Mmmm pro-pro-phosphoryl orthophosphate-phosphoric acid phosphate-phosphoric acid phosphoric acid 1 Inventive Example 31 Inventive Example 33 Inventive Example 33 Comparative Example 26 Comparative Example 27 Inventive Example 35 Comparative Example 28 yr) oo ON sm («+ &lt;) / i) =/.xAu+mi) / (ο) =9χ &lt; (u+m+v) / (! d) =ςχΑρα) / (&gt;ω)=inchχ · (ρα) / (υγΓηχ - (lo+lm+l&lt;) / (ιυ) =3xlAlu+lm+kM) / s) &quot;IX {:※ 201219599 斗1必1崦] sCNlECliH-(Nlo&lt;N:s[nHr_ special class ««iEra helmet^黯siNe inch ειοοι 移脉)) u-asso inch I-&lt;Ni (W) solid content 1 〇 II ο ο ο ο Ο ο o o o Ο ο o o 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1寸 寸 τ τ & Η Η Η — ϋ — — — — — — — — — — 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 5 Ξ 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 : Ε Ε Ε Ε £: E ξ. w V conversion % inch Ο inch 寸 inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch ο inchΟ IT) ω ω ω Ξ Ξ S Ξ ω ω τ-Η ω Ξ Ξ ω Ξ Ξ Ξ Ξ WW /-~NQ Ti conversion τ-Η Ο τ«~Η ί-Η ί-Η 1F«H ί-Η Type inch QQQ Ρ 1 ι Η QQQQ Ο ^-Η Ρ Q Τ-Η Q »«Η Q » ι Η Q 1-Η QQQ ί-Η Q Η Q ι—Η Q /-~N u N—/ Solid content S § S § S g S § § § § S gs § § S Type m &lt; r* -H Ο *—Η υ _Η Ο U υ y-^ υ υ Ο Ο U u iH u Η υ »-Η Ο &gt;—Η Ο υ υ CQ Solid content ν〇—Η ν〇Ό ο \〇' sQ Ό ν〇^&quot;Η CN &lt; y-^ PQ CQ Ξ PQ ΡΟ Ρ0 CQ Τ-Η PQ &gt;·Η 03 1—^ CQ m CQ CQ ffl CN CQ m CQ inch CQ «Ο CQ CQ /^ N c Solid content A inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch inch piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece piece case &lt;&lt; to ί-Η &lt;\〇&lt;&lt; 00 &lt;&lt; ί - Η » - Η &lt; 例 Example 36 Comparative Example 29 Comparative Example 30 Comparative Example 31 Comparative Example 32 1 Comparative Example 33 1 invention Example 37J Inventive Example 38 Inventive Example 39 Inventive Example 40 Comparative Example 34 1 1 Comparative Example 35 1 Ratio Example 36 1 Comparative Example 37 Comparative Example 38 Inventive Example 41 Inventive Example 42 Comparative Example 39 Comparative Example 40 Inventive Example 43 1 ίο 〇〇 VO $ Ο CN Ρ in 〇〇σ&gt; g 〇〇ΓΟ 00 201219599 raZItrcI Strong tNl 0&lt;Ν :ΠΠΠΠ3Ι 举讲ΗΓ }骧観骧観_Ka 饀扒#-黯s ζ ε inch ε I ο 〇1 moving _υΛςεοο inch 〇 oo ο 射 grease emulsion, (C): decane coupling agent, 1 1 1 II寸 inch inch inch inch inch Ό inch α 寸 Ο '-Ο ο E: CN| 13⁄4 CN PU, inch d inch o inch ο inch ο inch Ο r—&lt; ω CN ω &lt;Ν ω CN ω (Ν mr*HT·^ »-Η ¥·Ή rH QT*~&lt; Q Η QQ Ί-^ Q § s % § o U &gt;«Η CJ 塯绪±1 Jj/M Μ 铿m Ό Ό ν〇03 PQ CQ »&quot;-Η PQ CQ inch inch inch 奄&lt; r·^ C &lt;&lt; rH c Comparative Example 41 I 丨 invention example 44 invention example 45 I invention example 45 invention example 46 system 4 ^ Me, / to 00 〇0 00 00 Zhao Youwei: (Μ) &lt;审^: (ογ者咖和饀琨:(d) *港咖与岭《筚s : (Η) *者^^呤溆銮Celluloid: (&lt;1) 201219599 mtNl 叨一壮 (Ν Οζ: Step on 0Π3Ι_ ο Speak 3!_鹱«Destroy * Helmet ^-5-黯ο 8(Ν£17εΙ00Ι*脉 u-asso 寸斗&lt;N_&lt;NI&lt;〕 -&lt; (X7) 〇〇〇ο o 〇ο ο Ο Ο 〇〇ο ο ο 〇〇〇ο ο ο ο o (X6) 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 ι 0.050 0.057 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.048 0.050 0.050 0.050 (X5) 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 ! 0.0075 0.0075 0.0075 0.0075 0.0075 | 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.0075 0.008 0.000 0.000 0.40 0.40 0.40 0.40 ! 0.40 i 0.40 0.43 1 0.40 1 0.40 0.40 | 0.40 | 0.40 1 0.40 1 1 0.40 0.40 0.40 0.37 0.40 0.40 0.40 0.40 0.40 0.40 (X3) § § § % § s § § δ § δ S yn § (X2) 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 ί 丨 0.71 ^1 0.75 0.75 ! 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.76 0.75 0.75 0.75 (XI) 0.20 0.20 0.20 0.20 0.20 0.20 ! 1 0.20 1 1 0.20 1 1 0.13 1 | 0.23 I 0.20 0.20 1 0.20 1 1 0.20 1 1 0.20 1 0.20 0.20 0.20 0.20 0.19 0.20 0.20 0.20 pHIn inch' in — in — νη IT) — ¥ inch· ir&gt; in inch 'in inch · w-ϊ inch_in — other wt% m cn m CO ΓΛ mm ΓΛ m ΓΟ cn mm cn m CO mmm type orthophosphoric acid Pro-phosphoric acid phosphogen prophosphate phosphate phosphatase phosphatase phosphatase phosphatase phosphatase phosphatase phosphatase prophosphate phosphate phosphatidyl phosphate phosphatidyl phosphate phosphatase 29 Comparative Example 30 Comparative Example 31 Comparative Example 32 Λ Comparative Example 33 Inventive Example 37 Inventive Example 38 Inventive Example 39 Inventive Example 40 Comparative Example 34 Comparative Example 35 Comparative Example 36 Comparative Example 37 Comparative Example 38 1 Inventive Example 41 1 Inventive Example 42 Comparison Example 39 Comparative Example 40 Inventive Example 43 Comparative Example 41 Inventive Example 44 Inventive Example 45 No. 52 v〇00 $ Ο CN cn jn 〇〇〇\ § 00 00 cn 00 OO v〇00 6 inch 201219599 mzlncl Strong CSI 0 (N :a&gt;[n3r _ Piece Hi _ 鹱s _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Ο ο ο ο ο 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Original acid phosphate Inventive Example 45 Inventive Example 46 5 〇〇00 (ο) = 9x*(u+m+&lt;) / (ij) = ςχΛρ8/ (&gt;3)=inch X &lt; (PQ) / (Ιο) = £ xIAlu+lm+l&lt;) / (ιυ) =lrNIxIAlu+lm+l&lt;f) / (lm) =ΙΧ (※一ce+v) / ί) =/.χΑυ+ΐ&lt;) / 201219599 40035pifl is 100134328 No. Chinese manual, no correction, this revision period: January 12, 2012 [Table 13-1] Table 13-1 No. Plated steel sheet drying temperature °c Adhesion amount g/m2 Remark 1 Inventive Example 1 GF1 100 1.0 2 Inventive Example 2 GF1 100 1.0 3 Inventive Example 3 GF1 100 1.0 4 Comparative Example 1 GF1 100 1.0 5 Inventive Example 4 GF1 100 1.0 6 Inventive Example 5 GF1 100 1.0 7 Comparative Example 2 GF1 100 1.0 8 Comparative Example 3 GF1 100 1.0 9 Comparative Example 4 GF1 100 1.0 10 Comparative Example 5 GF1 100 1.0 11 Comparative Example 6 GF1 100 1.0 12 Comparative Example 7 GF1 100 1.0 Reference Japanese Patent No. 3883831 No. 13 Comparative Example 8 GF1 100 1.0 14 Comparative Example 9 GF1 100 1.0 Reference Japanese Patent Laid-Open No. 2006-152436 No. 15 Inventive Example 6 GF1 100 1.0 16 Inventive Example 7 GF1 100 1.0 17 Inventive Example 8 GF1 100 1.0 18 Inventive Example 9 GF1 100 1.0 19 Comparative Example 10 GF1 100 1.0 20 Inventive Example 10 GF1 100 1.0 21 Inventive Example 11 GF1 100 1.0 22 Comparative Example 11 GF1 100 1.0 23 Comparative Example 12 GF1 100 1.0 24 Inventive Example 12 GF1 100 1.0 25 Inventive Example 13 GF1 100 1.0 26 Comparative Example 13 GF1 100 1.0 27 Comparative Example 14 GF1 100 1.0 28 Inventive Example 14 GF1 100 1.0 29 Inventive Example 15 GF1 100 1.0 30 Comparative Example 15 GF1 100 1.0 31 Inventive Example 16 GF1 100 1.0 32 Comparative Example 16 GF1 100 1.0 33 Comparative Example 17 GF1 100 1.0 34 Comparative Example 18 GF1 100 1.0 35 Inventive Example 17 GF1 100 1.0 36 Inventive Example 18 GF1 100 1.0 37 Comparative Example 19 GF1 100 1.0 38 Inventive Example 19 GF1 100 1.0 39 Comparative Example 20 GF1 100 1,0 40 Inventive Example 20 GF1 100 1.0 51 201219599 40035pifl is the Chinese manual of No. 100134328. There is no underline correction. This revision date: January 12, 2012 Inventive Example 21 GF1 100 1.0 42 Inventive Example 22 GF1 100 1.0 43 Inventive Example 23 GF1 100 1.0 44 Inventive Example 24 GF1 100 1.0 45 Inventive Example 25 GF1 100 1.0 46 Inventive Example 26 GF1 100 1.0 47 Inventive Example 27 GF1 100 1.0 52 201219599 40035pifl No Chinese Patent Specification No. 100134328 Line revision date of this revision: January 12, 2012 [Table 13-2] Table 13-2 No. Plated steel plate drying temperature °c Adhesion amount g/m2 Remark 48 Comparative Example 21 GF1 100 1.0 49 Comparative Example 22 GF1 100 1.0 50 Inventive Example 28 GF1 100 1.0 51 Inventive Example 29 GF1 100 1.0 52 Comparative Example 23 GF1 100 1.0 53 Comparative Example 24 GF1 - - Surface treatment liquid gelation, so the suspension test 54 Comparative Example 25 GF1 100 0.1 55 Inventive Example 30 GF1 100 0.3 56 Inventive Example 31 GF1 100 0.5 57 Inventive Example 32 GF1 100 1.3 58 Inventive Example 33 GF1 100 1.5 59 Comparative Example 26 GF1 100 2.0 60 Comparative Example 27 GF1 40 1.0 61 Inventive Example 34 GF1 60 1.0 62 Inventive Example 35 GF1 140 1.0 63 Comparative Example 28 GF1 220 1.0 64 Inventive Example 36 GF1 100 1.0 65 Comparison Example 29 GF1 - - produced undissolved matter, so the test was discontinued. Comparative Example 30 GF1 - - produced undissolved matter, so the test was discontinued 67 Comparative Example 31 GF1 - - produced undissolved matter, so the test was discontinued 68 Comparative Example 32 GF1 100 1.0 69 Comparative Example 33 GF1 100 1.0 70 Inventive Example 37 GF1 100 1.0 71 Inventive Example 38 GF1 100 1.0 72 Inventive Example 39 GF1 100 1.0 73 Inventive Example 40 GF1 100 1.0 74 Comparative Example 34 GF1 - - Produced The solution was stopped, so the test was terminated. 75 Comparative Example 35 GF1 - - produced undissolved matter, so the test was aborted. 76 Comparative Example 36 GF1 - - produced undissolved matter, so the test was terminated 77 Comparative Example 37 GF1 100 1.0 78 Comparative Example 38 GFI 100 1.0 79 Inventive Example 41 GF1 100 1.0 80 Inventive Example 42 GF1 100 1.0 81 Comparative Example 39 GFI - - Amine ester resin agglomerated, so the test was stopped 82 Comparative Example 40 GF1 - - Amine ester resin was agglomerated, so the test was terminated 83 Inventive Example 43 GF1 100 1.0 84 Comparative Example 41 GF1 100 1.0 85 Inventive Example 44 GF2 100 1.0 86 Inventive Example 45 GF3 100 1.0 87 Inventive Example 45 GF4 100 1.0 88 Inventive Example 46 GF5 100 1.0 53 201219599 ππζιΠΙ: One belly (Nl 0 (N: s[n3r 乐挎3!乐fla destroy_ ifaίκ_^φ 黯ooze inch ei ο o yelling u-asso inch I-inch I&lt; lubricity (11) &lt;1 XXX &lt;3 &lt;&lt;1&lt;&lt;]&lt;]&lt;3 XX &lt;&lt;&lt;&gt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&gt; XX ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Liquid stability (9) Appearance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ &lt;3 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X ◎ ◎ ◎ ◎ X ◎ ◎ ◎ After application of degreasing ◎ ◎ ◎ ◎ t 1 〇 &lt; X ◎ ◎ X 〇t 1 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Heat-resistant discoloration/-N in ◎ 〇〇X ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 1 1 1 1 1 1 1 1 1 1 1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 N N弯 ◎ 1 〇 X ◎ ◎ ◎ XXX lt X X X X X X X / ^ N 平面 平面 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 1 invention example 2 invention example 3 comparison example 1 invention example 4 invention example 5 i comparison example 2 comparison example 3 i comparison example 4 comparison example 5 comparison example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Inventive Example 6 1 Inventive Example 7 Inventive Example 8 Inventive Example 9 Comparative Example 10 Inventive Example 10 Inventive Example 11 Comparative Example 11 6 2 (Ν m inch ΙΓ) 〇〇〇 〇〇〇 〇 Ν寸 inch V-Η ι/Ί 卜»-Η 〇〇〇\ CN 201219599 miNl sigh I strong 3 I otN: hi-fi 挎 挎 挎 _ _ « _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 &lt;1 X 1 〇 ◎ ◎ X 1 〇1 〇X ◎ ◎ &lt; 1 〇1 〇XX 1 〇 1 〇1 〇◎ ◎ &lt; 〇◎ ◎ X 〇+ 〇◎ ◎ ◎ _〇mm ¥ inch 1-HW Xin A3 inch life umbrella A3 ψ-η \〇m (N 00 (N On (N m 201219599 [31&lt ;] tnZIncI 壮 tsI0z: a&gt;B3I_ speak 3!#盘"|细细__饀^43黟〇〇2£寸£1001移脉 u-ageoo inch inch&lt; lubricityψ·^ &lt;3 &lt;&lt;3&lt;3&lt;3&lt;]&lt;]&lt;1&lt;1&gt; ◎ ◎ &lt;1 ο &lt;&lt;1&lt;&gt;&lt;&lt; Chemical agent gelation, so the test is stopped &lt;3 (10) ◎ ◎ ◎ 〇 &lt; ◎ ◎ ◎ 1 〇 1 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 1 〇 〇 〇 外观 外观 外观 外观 外观 X ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ N After degreasing ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ & ] - ◎ ◎ 〇〇 - - - - - - - - - - ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 姓 / ― ― ― ― ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ \ 〇t ◎ &lt; X /-~N CN ··&gt;*·^ Bending part ◎ 〇 ◎ ◎ ◎ 1 o X ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X t ◎ &lt;] X V_«-&quot; Plane ◎ ◎ ◎ ◎ ◎ 〇 X ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ I 〇〇t ◎ &lt; X , comparison 17 Comparative Example 18 Inventive Example 18 i Comparative Example 19 Inventive Example 19 i Comparative Example 20 Inventive Example 20 Inventive Example 21 Inventive Example 22 Inventive Example 23 Inventive Example 24 Inventive Example 25 Inventive Example 26 Inventive Example 27 Comparative Example 21 Comparative Example 22 Inventive Example 28 Inventive Example 29 Comparative Example 23 Comparative Example 24 Comparative Example 25 No. cn mmm oo ON ΓΛ o «-&lt; CO 5 JO 〇0 inch rs| - 201219599 En(NlnI:i^(NIO(N:siIIHr_ speaks Hrs鹱a壊«!1 Helmet 扒旮黟002 inch εΙ00Ι«®ιuuloso inch&lt;] 0 &lt;] &lt;3 &lt;&lt; 〇◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ] ] ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇〇 〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Food cn CO Army meal m 3 m 佥00 CN _〇in VO 00 〇\ S 201219599 mtNInc a strong (ΝΙ 0 (Ν:δ&gt;[π3Ι _ 柃3! #蕖«摧_ 扒 扒 _ _83£ inch £10 0 1濉|| UUSS0 inch [e丨 inchΙ&lt;] ε4ί Lubricity (Π) 1 &lt;] &lt;] &lt;3 &lt;1 &lt;1 &lt;&lt;]&lt;&lt;] ◎ Sweat 1 (10) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Liquid stability / -N N Appearance ◎ ◎ X ◎ ◎ ◎ ◎ ◎ X ◎ ◎ ◎ ◎ ◎ Solvent resistance οο ◎ Μ % -紊 紊 焕Since undissolved matter was generated in the production stage of the treatment liquid, the test was stopped and the undissolved product was stopped, so the test was stopped. ◎ ◎ ◎ ◎ ◎ L The undissolved product was dissolved. Therefore, the test i was stopped in the production stage of the treatment liquid. In the case of the undissolved product, the test was stopped. <, ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ' 未 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Μ 夺 咐 ◎ ◎ ◎ ◎ ◎ ◎ τ ΐ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ black resistance / ^ N inch ◎ fttll ml BJ 〇〇 ◎ ◎ ◎ f ml fftii 〇〇 ◎ ◎ ◎ ◎ ◎ corrosion resistance /*~Ν m \^/ After degreasing ◎ X 〇 ◎ ◎ 〇 ◎ X 〇 ◎ 〇 ◎ X ◎ Ν CN Bending part ◎ X &lt;] ◎ 〇 ◎ ◎ X &lt; ◎ ◎ ◎ &lt; ◎ N Plane ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Inventive Example 36 I Comparative Example 29 | Comparative Example 30 I | Comparative Example 31 ! |Comparative Example 32 ! Comparative Example 33 Inventive Example 37 Inventive Example 38 Inventive Example 39 1 Inventive Example 40 Comparative Example 34 Comparative Example 35 Comparative Example 36 Comparative Example 37 Comparative Example 38 I Inventive Example 41 Inventive Example 42 Comparative Example 39 Comparative Example 40 Inventive Example 43 Comparative Example 41 Inventive Example 44 6 Ό ίο 〇〇ο $ 〇fN in GO Os g (N 〇〇m 00 〇〇 201219599 s(Nl 叨i 壮 (Nl 0 (N: smHT table HTsfla «_Ka 扒 扒 - frnooiNe inch £ i ο oi 移 乌 u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 佥 佥 食 食 〇〇 0 〇〇 201219599 40035pifl Revision date: January 12, 2012 is the 100134134 As shown, the test steel sheets produced by using the surface treatment liquid of the present invention have excellent corrosion resistance (planar portion, processed portion, after degreasing), blackening resistance, heat discoloration resistance, and coating properties (after degreasing and degreasing) On the other hand, Comparative Example 1 (N〇4) outside the scope of the present invention has a content of the cationic amine ester resin emulsion (B) which is less than the range of the present invention. Therefore, corrosion resistance of the bent portion was not obtained at all, and heat resistance and lubricity were also poor. Comparative Example 2 (Νο·7) Since the content of the cationic amine ester resin emulsion (B) was outside the range of the present invention, the quality after alkali degreasing was poor. Resistant to dissolution The formulation did not satisfy the requirements. In Comparative Example 3 (Νο. 8) and Comparative Example 4 (Ν〇9), since the organic titanium chelate compound (D) according to the present invention was not formulated, the quality of the bent portion could not be obtained. In Comparative Example 5 (N〇1〇), 乂例7 (Νο·12), and Comparative Example 8 (No. 13) of the four-valent hunger compound (E), the resistance of the bent portion was not obtained. In the case of Comparative Example 6 (N. (1) The use of a pentavalent hunger compound was not able to obtain the peculiarity after degreasing at the bent portion, and the coating property after alkali degreasing was lowered. Comparative Example 9 (4) The tetravalent ruthenium compound (5) was used, but the amount of the cationic amine vinegar resin emulsion (8) exceeded the scope of the present invention, so it was not; the continuous bending and the addition of the king was resistant to the dissolution, and the comparative example 7 referenced the patent No. 3831 The zinc-zinc steel plate disclosed in the publication was tested, and the comparative example 9 was tested with reference to the zinc steel plate (10) of the Japanese Patent Laid-Open No. 2006-436. Dandan Γ Example 10 (Ν〇19) due to the Shixi sinter coupling agent (C) The solid content is not in the range of the present invention, so the miscibility is poor, and another aspect, the comparative example 201219599 40035pifl is the Chinese manual of No. 100134328. There is no slash correction. This revision date: January 12, 2012, 11 (N0.22) Since the above solid content is outside the scope of the present invention, the curvature of the JL portion cannot be obtained. Example 12 (Nq23) Since the solid content of the Wei coupler (C) for titanium of the organotitanium compound (9) is outside the range of the present invention, the resistance (N) (26) after degreasing is insufficient due to the above solid content. ::: 定:; Method for obtaining the resistance of the curved portion, the surface treatment liquid Ο Comparative Example 14 (ΝΟ·27) The amount of the tetravalent ruthenium compound (8) relative to the amount of titanium relative to the organic titanium chelating compound (8) is not Satisfy the circumference, so it does not play Xie Xiesheng's other aspects, Comparative Example 15 (the amount of Ν03= is beyond the scope of the present invention, so the durability after alkali degreasing and Comparative Example 16 (Νο. 32), Comparative Example 17 ( Ν〇33) From: The amount of molybdenum of the substance (F) does not satisfy the range of the present invention. (5) 4) The storage stability of the surface treatment liquid is poor due to the above-mentioned Ο. In Comparative Example 19 (No. 37), the amount of fluorine as 1(6) of the present invention was less than the range of the invention of the present invention, and therefore, Comparative Example 20 (Να39) was inferior in corrosion resistance due to the above-described range of _%. In the present invention, Comparative Example 22 (Ν〇.49) to Comparative Example 23 (NO.S2) which was not adjusted to an appropriate value of ρΗ could not be obtained. Comparative Example 24 with high enthalpy value (the gelation of the smashing part of the work can not be tested. The surface treatment liquid condensate 61 201219599 40035pifl is the Chinese manual of No. 100134328 without a slash correction this revision date _· January 2012 In Comparative Example 25 (No. 54) on the 12th, since the adhesion amount of the film did not satisfy the range of the present invention, sufficient resistance to the surname was not obtained. Further, in Comparative Example (No. 59), the adhesion amount of the film exceeded the scope of the present invention. The coating property was lowered. In Comparative Example 27 (No. 60), since the drying temperature did not satisfy the range of the present invention, the durability and the coating property after degreasing could not be obtained. Further, Comparative Example 28 (No. 63) was When the drying temperature is outside the range of the present invention, the silver resistance or the coating property of the bent portion is lowered. About the resin compound (A), Comparative Example 29 (Νο·65), Comparative Example 30 (Νο. 66), and Comparative Example 34 The carbon number of the fluorenyl group in (Νο. 74) and the comparative example % (Ν〇75) is outside the scope of the present invention, and the substitution number of the comparative example 3丨 (ν〇67 Comparative Example 36 (No. 76) t Ζ group The average wealth meets the scope of the Ming, so it is produced in the production stage of the surface treatment liquid. In the case of Comparative Example 32 (Νο·69) and Comparative Example 37 (Ν〇·77), since the average value of z = substitution number exceeded the value of the present invention, the corrosion resistance after the soil part and the alkali degreasing could not be obtained. Comparative Example 33 (N〇69), mouth (10)·Because the flatness of the Z-base is beyond the curvature of this turn, the corrosion resistance and storage stability of the bent portion of 38 are poor. Therefore, Comparative Example 39 (No. 81) towel amine vinegar resin emulsion The amine-lipid emulsion in column 4 () (M) is an anion in the preparation stage of the surface treatment liquid. (4) The purpose is to agglomerate. Therefore, (No. 84) is resistant to corrosion by the Wei coupling agent after the degreasing of the 歹41 alkali of the present invention. Sex. No access to [industry availability] 62 201219599 4UU35pifl No. 100134328 Chinese manual without scribe correction This revision period: January 12, 2012 曰 According to the present invention, a chromate can be supplied without The surface-treated plated steel sheet which is excellent in heat resistance, applicability, solvent resistance, and kinematic resistance is excellent in corrosion resistance (especially after bending and alkali degreasing). [Simplified description of the drawing] None. [Main component symbol description] 63 201219599 4UUJ5pifl For the Chinese manual No. 100134328, there is no slash correction. This revision date: January 12, 2012 invention patent specification (The format, order and bold text of this manual, please do not change it arbitrarily, please do not fill in the ※ part) ※ Application No.: 丨※ Application Date: Classification: I. Name of the invention: (Chinese/English) Surface treatment liquid for galvanized steel sheet and galvanized steel sheet and its manufacturing method SURFACE TREATMENT LIQUID FOR ZINC OR 0 ZINC ALLOY PLATED STEEL SHEET, ZINC OR ZINC ALLOY PLATED STEEL SHEET, AND METHOD OF PRODUCING THE STEEL SHEET II. SUMMARY OF THE INVENTION According to the present invention, a specific resin compound having a bisphenol skeleton, a cationic amine ester resin emulsion, and the like are formulated in respective predetermined ratios. a decane coupling agent, an organic chelating compound, a tetravalent cerium compound, a ceric acid compound, a fluorine compound, and water, and the pH is set to 4 to 5, and a bending process capable of forming a steel sheet on the surface of the metal cerium material can be obtained. Department of money, solvent resistance, applicability after alkali degreasing, and sweat resistance The chromium-free surface treatment liquid. Abstract: In particular, the invention, a specific resin, a bisphenol frame, a cationic urethane resin emulsion, a silane coupling agent, an organic titanic chelate compound, a tetravalent vanadium compound, a 1 201219599 4UUJ5pitl is 100134328 No. Chinese manual, no slash correction, date of revision: January 12, 2012, molybdic acid compound, a fluorine compound and water are mixed in accordance with the predetermined proportion, and the pH value is adjusted to 4 to 5. later, a chrome The membrane has excellent corrosion resistance in the bending part of the steel plate, solvent resistance, coating ability after alkali degreasing, and perspiration resistance. 201219599 40035pifl Amendment date: January 12, 2012 is No. 100134328 Chinese manual No picture jj line correction This is the scope of application: L A surface treatment for galvanized steel The following components are contained in a range satisfying the following conditions (1) to (6), and the value is 4 to 5: a resin compound having a bisphenol skeleton represented by the following general formula (I) ( A); a cationic amine ester resin emulsion (B) having at least one cationic functional group selected from the group consisting of a primary amino group to a tertiary amino group and a quaternary ammonium salt group; having an amine group selected from active hydrogen-containing groups, At least one of an epoxy group, a fluorenyl group, and a methacryloxy group, more than one type of cyclamate (C); an organic titanium chelating compound (D); a tetravalent compound (E) a molybdic acid compound (F); a fluorine compound (G); and water (H); (1) a solid relative to the above resin compound (A), the above cationic amine = fat emulsion (8), and the above-mentioned Wei coupling agent (c) In total, the solid content (Bs) of (As) + (Bs) + (Cs)}, the above cationic amine vinegar resin emulsion is calculated by weight ratio [(Bs) / {(As) + (Cs)}] Is a total of 0.10 to 0.30; S) t (2) with respect to the solid content of the above resin compound (A), the above cationic amine, resin emulsion (B) and the above-mentioned Wei coupling agent (c) Set {(As) + (Bs) + (cs)}, the above-mentioned decane coupling agent solid 64 201219599 40035pifl is the 10013434328 Chinese manual without a slash correction. Amendment date: January 12, 2012 body composition (0; ) is 0.60 to 0.85 by weight ratio [((^)/{(人)+(63) + ((^)})); (3) relative to the above-mentioned organic chelate compound (D) DTi), the solid content (Cs) of the above decane coupling agent (c) is 50 to 70 in terms of a weight ratio {(Cs) / (DTi)}; (4) relative to the above-mentioned organic titanium chelate compound (D) In terms of titanium (DTi), the vanadium equivalent amount (Ev) of the above-mentioned tetravalent vanadium compound (E) is 〇.30 to 0.50 in terms of the weight ratio {(Ev) / (DTi)}; (5) relative In the total solid content of the resin compound (a), the cationic amine vinegar resin emulsion (B), and the decane coupling agent (C), {(As) + (Bs) + (Cs)}, the above molybdic acid compound ( Indium converted amount of ρ) (FM. ) is 0.003 to 0.03 in terms of a weight ratio [(FmJ/Raj + (Bs) + (Cs))]; (6) relative to the above resin compound (a), the above cationic urethane resin emulsion (B), and the above decane The total solid content of the coupling agent (c) is f = + (Bs) + (Cs)}, and the fluorine content of the above fluorine compound (G) is calculated by weight (Gf) by weight ratio [(GF) / {(As) + ( Bs) + (Cs)} is counted as 0.01~0.1; S [Chemical 1] H3c-c-chs She-I OH Λ 65 201219599 40035pifl _ Date of revision: January 12, 2012 is No. 100134328 Chinese manual No slash correction In this formula (1), 1 and 1 respectively bonded to the benzene ring The z-group represented by the formula (II) or the formula (III) which is independently a hydrogen atom or the following, the average number of substitutions of the Z group per one benzene ring is 〇2 to 丨〇; n represents 2~ An integer of 50; [Chemical 2] CHjrN\ [Chemical 3] ◎ —CH2~N^—R4 aTM ···(【&quot;) In equations (II) and (III), R!, ruler 2, chemistry, 114, and 115 are independent of each other. A hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a light-based alkyl group having 1 to 10 carbon atoms, and A- represents a hydroxide ion or an acid ion. 2. The surface treatment liquid for galvanized steel sheets according to claim 1, wherein the surface treatment liquid further contains soil (W), relative to the above resin compound (A) and the above cationic amine energy resin emulsion ( The solid content of the B) is As(As) + (Bs)}, and the solid content (Ws) of the upper wax (W) is expressed by the weight ratio [(Ws)/{( as) + (bs))] In the range of 0.2 to 0.4. 66 201219599 40035pifl is the first face of the 3rd towel wing type makeup makeup date: March 12th of the year of the year 3. The method of manufacturing a galvanized steel sheet is characterized in that the surface treatment liquid described above is dried. After: Kauri becomes the mother's early surface 0.2 g / m ~ l 8 g / m2 on the surface of the coated steel plate, and then reaches the plate temperature of 5 (rc ~ 18 (rc for dry ^ "- Lin Lin steel, The surface treatment film having a surface of g/m to 1.8 g/m 2 per side is 0·2. The surface treatment film is applied as a surface treatment liquid of the crucible to the surface of the steel sheet, and It is obtained by drying at 180 ° C as described in 刭 and =. 伽· is 50 ° C~ 67 201219599 H-UUJ jpifl is the Chinese manual of No. 100134328. There is no slash correction. Revision date: January 12, 2012 IV. Designation of representative drawings: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: No 0 3